CN110423360A - A kind of ultrasonic wave added photocatalysis to selectively degradation condensed tannin and its palliating degradation degree control method - Google Patents
A kind of ultrasonic wave added photocatalysis to selectively degradation condensed tannin and its palliating degradation degree control method Download PDFInfo
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Abstract
The present invention provides a kind of ultrasonic wave added photocatalysis to selectively degradation condensed tannin and its palliating degradation degree control method, belong to natural polymer degradation field, the described method comprises the following steps: step 1) obtains condensed tannin from containing extraction in condensed tannin raw material；Condensed tannin is configured to aqueous solution by step 2), so that condensed tannin is degraded under the conditions of ultrasonic wave added photocatalysis the aqueous solution, interval time samples to obtain degradation solution；Step 3) controls degradation step 2 using formaldehyde combined techniques) palliating degradation degree, termination step 2) is reacted when the tannin in degradation solution no longer increases with the reacting dose of formaldehyde, obtains condensed tannin oligomer aqueous solution.Using the degradation condensed tannin of the method property of can choose of the invention, while its palliating degradation degree can be controlled, to obtain the polyphenol oligomer of ideal high added value.
Description
Technical field
The present invention relates to a kind of ultrasonic wave added photocatalysis to selectively degradation condensed tannin and its palliating degradation degree control method,
Belong to natural polymer degradation field.
Background technique
Predictable non-renewable fossil resource exhaust and it is prepared by the chemicals based on petroleum, coal and natural gas
The not biodegradable of the high energy consumption of journey and high pollution and its manufactured goods, forcing can not be again with renewable biomass resources substitution
Raw fossil resource, which prepares chemicals, becomes the Main way of future development.Tannin is the second-biggest-in-the-world yield for being only second to lignin
Plant polyphenol, the yield number of the annual tannin in the whole world in terms of hundred million tons (wherein condensed tannin account for the 90% of whole tannin yield with
On).Non-renewable petroleum phenol or coal tar phenols synthetic adhesive are replaced with reproducible vegatable tannin, is timber industry
With the hot spot of other industrial department growing interests.The actually condensed tannin conjunction that has been successfully applied to Artificial Plate Adhesive
At, and industrial applications are realized in countries and regions such as Australia, South Africa and South America, China also has developed phenol substitution
The larch tannin gluing agent of rate 60%, realizes popularization and application in the production of glued board, fiberboard and particieboard.Therefore from
Condensed tannin is started with, and the renewable resource substitution problem of Artificial Plate Adhesive synthesis material is solved, and is relatively real selection.
However, so far, condensed tannin can not still substitute synthesis of the phenol for based Wood Adhesives completely.Reason is tannin point
Son amount is big, reaction site causes the Storage period of tannin and active phase short more；It is equally because molecular weight is big, by molecular dimension and shape
The limitation of shape, the active position remained in molecule is because leading to gluing at a distance of too far or be embedded due to can not further participate in reaction
Intensity is low；Additionally, due to the extent of reaction with formaldehyde is not high and the presence of abundant residues hydrophilic radical, lead to tannin adhesive
Poor water resistance.
Since the fifties in last century, with tannin inoxidizability, Scavenging ability, inhibitory anti-virus performance, drop
The confirmation of the bioactivity such as blood lipid, research day of this kind of natural products in fields such as functional food, Chinese materia medica preparation, household chemicals
Benefit deeply, is more widely applied.Existing research show the low monomer of tannin middle-molecular-weihydroxyethyl or oligomer have stronger biology,
Chemical activity and pharmacological function.As tanning material in use, low molecular weight or oligomer tannin also embody better service performance.
The big key of tannin molecular weight is solved to be to degrade to tannin using suitable means.Currently, tannin is degraded
Method specifically include that oxidation degradation method, use with antozone, monatomic chlorine etc. be oxidant, such as use hydrogen peroxide, secondary chlorine
The rudimentary oxidant such as sour sodium, potassium chlorate, oxidation efficiency is low, there is the oxidizer residual being not readily separated in oxidation product；Acid degradation
Method, it is under strongly acidic conditions, acid strong using benzyl mercaptan as nucleopilic reagent degradation tannin, resistance to strong acid equipment need to be used, and benzyl mercaptan is not
It is easily separated with degradation product, while making degradation product with penetrating odor because of sulfur-bearing, strong acid is not easy to separate from degradation product；Alkali drop
Solution, the degradation amount very little of tannin, alkali are not easy to separate with degradation product；Biological degradation method, tannin inhibit microorganism with wide spectrum
Property, cause the microorganism of degradable tannin to select difficult, and microorganism is generally more preferable to tannin oligomer degradation effect, to height
Polymers effect is limited, and the microbial degradation time is long, low output, low efficiency；Sulphite degradation, only adds a large amount of sulfurous acid
Salt can just lead to a degree of degradation, and sulphite is blended in tannin degradation product and is not readily separated, and influence the use of tannin.
Chinese Patent Application No. 2004100226165, authorization date are that the application case on April 5th, 2006 discloses one kind
Vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, tannin product, and this method uses the tannin extracting solution of acquisition
Different solvent extractions, then carry out catalytic hydrogenolytic cleavage and obtain polyphenol monomer and oligomer.Although the method energy of this application
Enough overcome oxidation material to be difficult to isolated defect with product, however there is degradation by the way of catalytic hydrogenolytic cleavage not enough or drop
Excessive problem is solved, the ideal polyphenol monomer of selective acquisition and oligomer are relatively difficult to achieve.
Summary of the invention
1. to solve the problems, such as
For the defect for the degradation selectivity that cannot achieve condensed tannin in the prior art, it is super that the present invention provides one kind
The method that sound assists visible light degradation selectivity condensed tannin degradation selectivity and can control its palliating degradation degree, to obtain
Obtain the polyphenol oligomer of ideal high added value.
2. technical solution
The present invention provides a kind of ultrasonic wave added visible light degradation selectivity condensed tannin and its palliating degradation degree controlling parties
Method, comprising the following steps:
Step 1) obtains condensed tannin from containing extraction in condensed tannin raw material；
Condensed tannin is configured to aqueous solution by step 2), and the aqueous solution is made under conditions of ultrasonic wave added visible light
Condensed tannin is degraded, and interval time samples to obtain degradation solution；
Step 3) controls degradation step 2 using formaldehyde combined techniques) palliating degradation degree, to the tannin and formaldehyde in degradation solution
The reaction that step 2) is terminated when reacting dose no longer increases, obtains condensed tannin oligomer aqueous solution.
As further improvement of the present invention, the aqueous solution is placed in visible light in the step 2) or ultraviolet light is held
Under continuous irradiation, while ultrasound is carried out to aqueous solution, then visible light or ultraviolet light response type nanocatalyst are added into aqueous solution,
Hydrogen peroxide is added by several times, controls reaction temperature.
As further improvement of the present invention, the step 3) specific steps are as follows:
Sample of degrading 3-1) is divided into incipient degradation sample and processing degradation sample identical in quality, first dries incipient degradation sample
To constant weight, quality is denoted as M0；
Formalin 3-2) is added into processing degradation sample and hydrochloric acid solution obtains mixed solution, by mixed solution in oil
It is heated to reflux under the conditions of bath, reacts tannin sufficiently with formaldehyde, and keep the leakproofness of reaction system；
3-3) after reaction, it after whole system is cooled to room temperature, filters, obtain solid product, by solid product
It is placed in infrared baking oven and dries to constant weight, quality is denoted as M1, formaldehyde binding capacity F, calculation formula are as follows: F=(M are calculated according to formula1-
M0)/M0, stop degradation reaction when formaldehyde binding capacity F no longer changes.
As further improvement of the present invention, step 3-3) in, stop when the formaldehyde binding capacity of degradation product no longer increases
It only degrades, is cooled to room temperature, obtain ultrasonic wave added photocatalytic degradation condensed tannin oligomer aqueous solution, the aqueous solution is through negative pressure
Vacuum freeze drying obtains being easy to methylolated tannin polyphenol oligomer powder after Rotary Evaporators evaporate moisture content.
As further improvement of the present invention, the visible-light response type nano catalyst include nano tungsten trioxide,
In nano cuprous oxide, nanometer bismuth oxyiodide, Nano cadmium sulphide, nano-copper sulfide, nanometer pucherite and nano ceric oxide
It is one or more of；The ultraviolet light response type catalyst includes nano-titanium dioxide, nanometer bismuth phosphate, nano-calcium carbonate silver, nanometer
Tin oxide, nanometer α-one or more of di-iron trioxide or nano zine oxide.
As further improvement of the present invention, the mass concentration of aqueous solution is 2~20% in the step 2), described super
Acoustic power is 500~2000W.
As further improvement of the present invention, the addition quality of the visible light or ultraviolet light response type catalyst is water
The 0.5~9% of tannin quality in solution.
As further improvement of the present invention, the step 2) hydrogen peroxide accounts for the 5~50% of tannin quality, reaction
At 20~100 DEG C, the concentration of hydrogen peroxide is 30~50% for temperature control.
As further improvement of the present invention, the mass concentration of the formalin is 36.4~37.5%, hydrochloric acid
Solution concentration is 10mol/L.
As further improvement of the present invention, the step 1) specifically:
The plant material that 1-1) will be enriched in condensed tannin is dry, is then comminuted into plant powder；
1-2) plant powder is placed in a series of methanol/acetone aqueous solution of various concentrations, plant powder exists first
Profit is carried out in methanol/acetone aqueous solution to rise；
It 1-3) successively extracts in the methanol/acetone aqueous solution under ultrasonic wave auxiliary in increasing concen-trations, is successively filtered by vacuum
Leaching liquor is obtained, obtains condensed tannin through evaporation recycling design, vacuum freeze drying after leaching liquor is merged.
As further improvement of the present invention, the step 1-2) in a series of various concentrations methanol/acetone it is water-soluble
Liquid includes 50%, 60%, 70%, 80% strength solution.
As further improvement of the present invention, the step 1-2) in plant powder and methanol aqueous solution mass mixing
Than for 1:(10~60), profit time of rising is 2~5h.
As further improvement of the present invention, the step 1-3) in 100~500W of ultrasonic power, extraction temperature is
30~90 DEG C, ultrasonic 0.5~1.5h of extraction time.
As further improvement of the present invention, the step 1-1) in degree of drying be moisture content 12% hereinafter, described
The partial size of plant powder is 100 mesh or less.
As further improvement of the present invention, the plant material rich in condensed tannin includes Black Wattle, acacia rachii
Skin, bark of dahurian larch, jack pine bark, spruce bark, hemlock bark, red root bark, phyllanthus emblica bark, Chinese waxmyrtle bark, Albizzia kalkora tree
In skin, horse-tail bark, principal columns of a hall tree bark, willow bark, the red hard wooden timber, radix ephedrae, garden sorrel root, treaster and dye yam stem tuber
It is one or more of.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) ultrasonic wave added photocatalysis to selectively of the invention degradation condensed tannin and its palliating degradation degree control method, it is first
First under visible light or ultraviolet light using photoresponse type catalyst generate hydroxyl radical free radical, ultra-oxygen anion free radical,
Photohole and light induced electron act on the degradation reaction of condensed tannin, the combined oxidation reaction that several substance collaborations generate
Oxidability is strong, oxidation efficiency is high, greatly promotes efficiency, while can make this under ultrasonic wave subsidiary conditions
Oxidant, catalyst in system and the hydroxyl radical free radical of generation, ultra-oxygen anion free radical, photohole and light induced electron
More evenly, furthermore the cavitation of ultrasonic wave has Mechanochemistry for equal dispersions, further increases degradation efficiency, is efficiently dropping
It recycles formaldehyde combined techniques to control reaction under the conditions of solution, on the one hand guarantees the degradable of tannin, on the other hand avoid
Excessive degradation finally obtains the product with high added value.
(2) ultrasonic wave added photocatalysis to selectively of the invention degradation condensed tannin and its palliating degradation degree control method, are adopted
Use formaldehyde as the selective agent of degradation object, according to the hydroxymethylation principle of condensed tannin and formaldehyde, only measurement with
Formaldehyde is easy to carry out the degradation product of hydroxymethylation, avoids the interference of other degradation products, has apparent selectivity, passes through
Formaldehyde binding capacity variation tendency is tracked, stops degradation when formaldehyde binding capacity no longer increases, avoids the excessive degradation of tannin, from
And effectively select to obtain polyphenol quasi-oligomer, it can smoothly be applied to the synthesis of Artificial Plate Adhesive, tanning and medicine
Equal fields.
(3) ultrasonic wave added photocatalysis to selectively of the invention degradation condensed tannin and its palliating degradation degree control method, drop
Light photoresponse type catalyst can be separated from degradation product solution by high speed centrifugation after the reaction was completed, be recycled, degradation
The waste discharge of the non-hazardous environment of process belongs to clean manufacturing and Green Chemistry field, and there is no oxidants and photoresponse type to be catalyzed
Agent separates difficult problem with degradation product, will not pollute degradation product, there is no issues of purification when degradation product subsequent applications.
(4) ultrasonic wave added photocatalysis to selectively of the invention degradation condensed tannin and its palliating degradation degree control method, lead to
Crossing pretreatment can be from Black Wattle, yearning between lovers bark, bark of dahurian larch, jack pine bark, spruce bark, hemlock bark, red root
Bark, phyllanthus emblica bark, Chinese waxmyrtle bark, Albizzia kalkora bark, horse-tail bark, principal columns of a hall tree bark, willow bark, red hard wooden timber, Chinese ephedra
In 18 kinds of plant materials such as root, garden sorrel root, treaster and dye yam stem tuber recycling obtain more utility values Polyphenols it is oligomeric
Object, this method have generality, have a wide range of application.
Detailed description of the invention
Fig. 1 is the Maldi-Tof-MS map before the larch tannin degradation in embodiment 3；
Fig. 2 is the gpc chromatogram before the larch tannin degradation in embodiment 3；
Fig. 3 is the Maldi-Tof-MS map after the larch tannin degradation in embodiment 3；
Fig. 4 is the gpc chromatogram after the larch tannin degradation in embodiment 3.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
The present embodiment is the embodiment using method processing Black Wattle of the invention:
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the Black Wattle of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:10, moistens the time 2h that rises every time, respectively extracts 1 time under ultrasonic power 100W auxiliary,
Extraction temperature is controlled at 30 DEG C, and ultrasound extraction time 0.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains black wattle bark tannins after Rotary Evaporators evaporate solvent.
Black wattle bark tannins are configured to the aqueous solution of 2% concentration, are placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 500W, quartz reaction kettle is placed under the ultraviolet light irradiation of 500W, then the tannin into reaction kettle
Mass fraction 0.5% (in terms of tannin quality) visible-light response type nano catalyst is added in tannin aqueous solution in aqueous solution to receive
Rice tungstic acid (WO3), then the hydrogen peroxide (H for accounting for tannin quality 5% is continuously added into tannin aqueous solution into reaction kettle2O2),
The concentration of hydrogen peroxide is 30%, and every 1h is added 1 time, and reaction temperature controls at 20 °C, carries out ultrasonic wave added visible light drop
Solution reaction；
In degradation process, every 1h takes mixture 1 time of degradation sample and visible-light response type nano catalyst, high speed centrifugation point
Remaining degradation sample after visible-light response type nano catalyst is separated out, degradation sample is divided into 4 parts, guarantees every part of 5.00g (measured value essence
Really arrive 2 significant digits), wherein 1 part is placed in infrared baking oven and dries to constant weight, quality is denoted as M0, remaining 3 parts are shifted respectively
Into 3 single-necked flasks of the 150mL with reflux condensing tube, into each single-necked flask, (measured value is accurate to small addition 10.00g
Two after several points) formalins of 36.4~37.5% mass concentrations and 5mL concentration is 10M hydrochloric acid solution, mixed solution exists
It is heated to reflux 30min under the conditions of 120 DEG C of oil bath, reacts tannin sufficiently with formaldehyde, and ensures the leakproofness of entire reaction system.
After reaction, after whole system is cooled to room temperature, tannin and formaldehyde reaction system are filtered, what acquisition tannin was reacted with formaldehyde consolidates
Body product, solid product is placed in infrared baking oven and is dried to constant weight, and measuring the quality of solid product, (measured value is accurate to
2 significant digits), which is denoted as M1.Formaldehyde binding capacity is denoted as F, calculation formula are as follows: F=(M1-M0)/M0。
3 times measurement result is averaged, and is stopped degradation when the formaldehyde binding capacity of degradation product no longer increases, is cooled to room
Temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer aqueous solution, which evaporates through negative pressure Rotary Evaporators
Vacuum freeze drying obtains being easy to methylolated tannin polyphenol oligomer powder after falling moisture content.
Formaldehyde binding capacity no longer increases after reaction 11h, stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic
Condensed tannin oligomer aqueous solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain list
Peaceful polyphenol oligomer powder.The maximum formaldehyde binding capacity of the degradation product is 0.91, and the formaldehyde binding capacity before degradation is 0.36.
Embodiment 2
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the yearning between lovers bark of moisture content 10%, is ground into plant pulverizer
The plant powder of 110 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:60, moistens the time 5h that rises every time, respectively extracts 1 time under ultrasonic power 500W auxiliary,
Extraction temperature is controlled at 90 DEG C, and ultrasound extraction time 1.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains yearning between lovers Tannins From Barks after Rotary Evaporators evaporate solvent.
Yearning between lovers Tannins From Barks are configured to the aqueous solution of 20% concentration, are placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 2000W, quartz reaction kettle is placed under the visible light irradiation of 2000W, then into reaction kettle
Mass fraction 1% (in terms of tannin quality) visible-light response type nano catalyst nano cuprous oxide is added in tannin aqueous solution
(Cu2O), the hydrogen peroxide (H for accounting for tannin quality 50% is continuously added into the tannin aqueous solution then into reaction kettle2O2), hydrogen peroxide
Concentration is 50%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 100 DEG C, carries out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 6h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
Maximum formaldehyde binding capacity is 0.91 after the condensed tannin extracting solution is degraded, and the formaldehyde binding capacity before degradation is 0.41.
Embodiment 3
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the bark of dahurian larch of moisture content 8%, is ground into plant pulverizer
The plant powder of 120 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:20, moistens the time 2.5h that rises every time, respectively extracts 1 under ultrasonic power 200W auxiliary
Secondary, extraction temperature is controlled at 40 DEG C, every time ultrasound extraction time 40min, and leaching liquor, each leaching are filtered by vacuum to obtain after extraction
Extract merges, and vacuum freeze drying obtains bark of dahurian larch tannin after Rotary Evaporators evaporate solvent.
Bark of dahurian larch tannin is configured to the aqueous solution of 4% concentration, is placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 600W, quartz reaction kettle is placed under the visible light irradiation of 700W, then the list into reaction kettle
Mass fraction 1.5% (in terms of tannin quality) visible-light response type nano catalyst nano bismuth oxyiodide is added in peaceful aqueous solution
(BiOI), the hydrogen peroxide (H for accounting for tannin quality 5% is continuously added into the tannin aqueous solution then into reaction kettle2O2), hydrogen peroxide
Concentration is 30%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 30 DEG C, carries out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 8h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
Maximum formaldehyde binding capacity is 0.79 after the condensed tannin extracting solution is degraded, and the formaldehyde binding capacity before degradation is 0.42.
Structural identification is carried out for the condensed tannin before degradation, Fig. 1 is the Maldi-Tof- before larch tannin degradation
MS map；Fig. 2 is the gpc chromatogram before larch tannin degradation；
Structural identification is carried out for obtained tannin polyphenol oligomer simultaneously, Fig. 3 is after larch tannin is degraded
Maldi-Tof-MS map；Fig. 4 is the gpc chromatogram after larch tannin degradation.According to above-mentioned graphic comparison it is found that utilizing this hair
Condensed tannin is finally degraded into condensed tannin oligomer by bright method, to greatly improve its utility value.
Embodiment 4
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the jack pine bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 130 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:30, moistens the time 3h that rises every time, respectively extracts 1 time under ultrasonic power 300W auxiliary,
Extraction temperature is controlled at 50 DEG C, every time ultrasound extraction time 50min, and leaching liquor, each extraction are filtered by vacuum to obtain after extraction
Liquid merges, and vacuum freeze drying obtains jack pine Tannins From Barks after Rotary Evaporators evaporate solvent.
Jack pine Tannins From Barks are configured to the aqueous solution of 6% concentration, are placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 700W, quartz reaction kettle is placed under the visible light irradiation of 900W, then the list into reaction kettle
Mass fraction 2% (in terms of tannin quality) visible-light response type nano catalyst nano cadmium sulfide (CdS) is added in peaceful aqueous solution,
Hydrogen peroxide (the H for accounting for tannin quality 50% is continuously added into the tannin aqueous solution into reaction kettle again2O2), the concentration of hydrogen peroxide is
50%, every 1h is added 1 time, and reaction temperature controls under the conditions of 40 DEG C, carries out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 6h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 0.92, and the formaldehyde binding capacity before degradation is 0.37.
Embodiment 5
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the spruce bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:40, moistens the time 3.5h that rises every time, respectively extracts 1 under ultrasonic power 400W auxiliary
Secondary, extraction temperature is controlled at 60 DEG C, every time ultrasound extraction time 1h, and leaching liquor, each extraction are filtered by vacuum to obtain after extraction
Liquid merges, and vacuum freeze drying obtains spruce bark tannin after Rotary Evaporators evaporate solvent.
Spruce bark tannin is configured to the aqueous solution of 8% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 800W, quartz reaction kettle is placed under the visible light irradiation of 1100W, then the list into reaction kettle
Mass fraction 2.5% (in terms of tannin quality) visible-light response type nano catalyst is added in tannin aqueous solution in peaceful aqueous solution
Hydrogen peroxide (the H for accounting for tannin quality 5% is continuously added into nano-copper sulfide (CuS), then tannin aqueous solution into reaction kettle2O2),
The concentration of hydrogen peroxide is 30%, and every 1h is added 1 time, and under the conditions of reaction temperature is 50 DEG C, it is anti-to carry out ultrasonic wave added Visible Light Induced Photocatalytic
Answer, in degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 7h after formaldehyde combine
Amount no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer aqueous solution, should
Aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtains tannin polyphenol oligomer powder.The degradation product
Maximum formaldehyde binding capacity be 1.14, formaldehyde binding capacity before degradation is 0.54.
Embodiment 6
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the hemlock bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:50, moistens the time 4h that rises every time, respectively extracts 1 time under ultrasonic power 150W auxiliary,
Extraction temperature is controlled at 70 DEG C, every time ultrasound extraction time 70min, and leaching liquor, each extraction are filtered by vacuum to obtain after extraction
Liquid merges, and vacuum freeze drying obtains hemlock bark tannin after Rotary Evaporators evaporate solvent.
Hemlock bark tannin is configured to the aqueous solution of 10% concentration, is placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 900W, quartz reaction kettle is placed under the visible light irradiation of 1300W, then into reaction kettle
Mass fraction 3% (in terms of tannin quality) visible-light response type nano catalyst is added in tannin aqueous solution in tannin aqueous solution
Nanometer pucherite (BiVO4), then the hydrogen peroxide for accounting for tannin amount quality 50% is continuously added into tannin aqueous solution into reaction kettle
(H2O2), the concentration of hydrogen peroxide is 50%, and every 1h is added 1 time, under the conditions of reaction temperature is 60 DEG C, carries out ultrasonic wave added visible light
Degradation reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 8h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.11, and the formaldehyde binding capacity before degradation is 0.43.
Embodiment 7
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the red root bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:15, moistens the time 4.5h that rises every time, respectively extracts 1 under ultrasonic power 250W auxiliary
Secondary, extraction temperature is controlled at 80 DEG C, every time ultrasound extraction time 80min, and leaching liquor, each leaching are filtered by vacuum to obtain after extraction
Extract merges, and vacuum freeze drying obtains red root Tannins From Barks after Rotary Evaporators evaporate solvent.
Red root Tannins From Barks are configured to the aqueous solution of 12% concentration, are placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 1000W, quartz reaction kettle is placed under the visible light irradiation of 1500W, then into reaction kettle
The catalysis of (in terms of the tannin quality) visible-light response type nano of mass fraction 3.5% is added in tannin aqueous solution in tannin aqueous solution
Agent nano ceric oxide (CeO2), then the dioxygen for accounting for tannin amount quality 50% is continuously added into tannin aqueous solution into reaction kettle
Water (H2O2), the concentration of hydrogen peroxide is 50%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 70 DEG C, carries out ultrasonic wave added
Visible Light Induced Photocatalytic reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 9h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.51, and the formaldehyde binding capacity before degradation is 0.46.
Embodiment 8
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the phyllanthus emblica bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:25, moistens the time 2h that rises every time, respectively extracts 1 time under ultrasonic power 350W auxiliary,
Extraction temperature is controlled at 35 DEG C, and ultrasound extraction time 0.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains phyllanthus emblica Tannins From Barks after Rotary Evaporators evaporate solvent.
Phyllanthus emblica Tannins From Barks are configured to the aqueous solution of 14% concentration, are placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 1100W, quartz reaction kettle is placed under the visible light irradiation of 1700W, then into reaction kettle
Mass fraction 4% (in terms of tannin quality) visible-light response type nano catalyst is added in tannin aqueous solution in tannin aqueous solution
Nano tungsten trioxide (WO3) hydrogen peroxide for accounting for tannin quality 40% is continuously added into the tannin aqueous solution into reaction kettle again
(H2O2), the concentration of hydrogen peroxide is 40%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 80 DEG C, and carrying out ultrasonic wave added can
Light-exposed degradation reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 6h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.32, and the formaldehyde binding capacity before degradation is 0.31.
Embodiment 9
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the Chinese waxmyrtle bark of moisture content 10%, is ground into plant pulverizer
The plant powder of 110 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the methanol aqueous solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:35, moistens the time 5h that rises every time, respectively extracts 1 time under ultrasonic power 450W auxiliary,
Extraction temperature is controlled at 45 DEG C, and ultrasound extraction time 1.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains Chinese waxmyrtle bark tannin after Rotary Evaporators evaporate solvent.
Chinese waxmyrtle bark tannin is configured to the aqueous solution of 16% concentration, is placed in supersonic generator, temperature controller
In quartz reaction kettle, ultrasonic power 1200W, quartz reaction kettle is placed under the visible light irradiation of 1900W, then into reaction kettle
The catalysis of (in terms of the tannin quality) visible-light response type nano of mass fraction 4.5% is added in tannin aqueous solution in tannin aqueous solution
Agent nano cuprous oxide (Cu2O), the hydrogen peroxide for accounting for tannin quality 30% is continuously added into the tannin aqueous solution then into reaction kettle
(H2O2), the concentration of hydrogen peroxide is 40%, and every 1h is added 1 time, under the conditions of reaction temperature is 90 DEG C, carries out ultrasonic wave added visible light
Degradation reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 7h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.21, and the formaldehyde binding capacity before degradation is 0.44.
Embodiment 10
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the Albizzia kalkora bark of moisture content 11%, is ground into plant pulverizer
The plant powder of 110 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and aqueous acetone solution is 1:10, moistens the time 2h that rises every time, respectively extracts 1 time under ultrasonic power 100W auxiliary,
Extraction temperature is controlled at 30 DEG C, and ultrasound extraction time 0.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains Albizzia kalkora Tannins From Barks after Rotary Evaporators evaporate solvent.
Albizzia kalkora Tannins From Barks are configured to the aqueous solution of 2% concentration, are placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 500W, quartz reaction kettle is placed under sunlight irradiation, then the tannin aqueous solution into reaction kettle
In tannin aqueous solution in be added mass fraction 5% (in terms of tannin quality) visible-light response type nano catalyst nano iodine oxidation
Hydrogen peroxide (the H for accounting for tannin quality 30% is continuously added into bismuth (BiOI), then tannin aqueous solution into reaction kettle2O2), hydrogen peroxide
Concentration be 40%, every 1h is added 1 time, and reaction temperature controls at 20 °C, carry out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic,
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 8h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.45, and the formaldehyde binding capacity before degradation is 0.66.
Embodiment 11
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the horse-tail bark of moisture content 9%, is ground into plant pulverizer
The plant powder of 130 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and methanol aqueous solution is 1:60, moistens the time 5h that rises every time, respectively extracts 1 time under ultrasonic power 500W auxiliary,
Extraction temperature is controlled at 90 DEG C, and ultrasound extraction time 1.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains horse-tail bark after Rotary Evaporators evaporate solvent.
Horse-tail Tannins From Barks are configured to the aqueous solution of 20% concentration, are placed in supersonic generator, temperature controller
Quartz reaction kettle in, ultrasonic power 2000W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle
Mass fraction 5.5% (in terms of tannin quality) visible-light response type nano catalyst is added in tannin aqueous solution in aqueous solution to receive
Hydrogen peroxide (the H for accounting for tannin quality 30% is continuously added into rice cadmium sulfide (CdS), then tannin aqueous solution into reaction kettle2O2),
The concentration of hydrogen peroxide is 40%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 100 DEG C, carries out ultrasonic wave added visible light drop
Solution reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 11h after stop
Formaldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer
Aqueous solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder
End.The maximum formaldehyde binding capacity of the degradation product is 1.33, and the formaldehyde binding capacity before degradation is 0.57.
Embodiment 12
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the principal columns of a hall tree bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and aqueous acetone solution is 1:20, moistens the time 2.5h that rises every time, respectively extracts 1 under ultrasonic power 200W auxiliary
Secondary, extraction temperature is controlled at 40 DEG C, every time ultrasound extraction time 40min, and leaching liquor, each leaching are filtered by vacuum to obtain after extraction
Extract merges, and vacuum freeze drying obtains principal columns of a hall tree Tannins From Barks after Rotary Evaporators evaporate solvent.
Principal columns of a hall tree Tannins From Barks are configured to the aqueous solution of 5% concentration, are placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 700W, quartz reaction kettle is placed under sunlight irradiation, then the tannin aqueous solution into reaction kettle
In tannin aqueous solution in be added mass fraction 6% (in terms of tannin quality) visible-light response type nano catalyst nano copper sulfide
(CuS), the hydrogen peroxide (H for accounting for tannin quality 5% is continuously added into the tannin aqueous solution then into reaction kettle2O2), hydrogen peroxide it is dense
Degree is 30%, and every 1h is added 1 time, is being stirred, and reaction temperature controls under the conditions of 30 DEG C, and it is anti-to carry out ultrasonic wave added Visible Light Induced Photocatalytic
It answers,
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 10h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.32, and the formaldehyde binding capacity before degradation is 0.58.
Embodiment 13
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the willow bark of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and aqueous acetone solution is 1:30, moistens the time 3h that rises every time, respectively extracts 1 time under ultrasonic power 300W auxiliary,
Extraction temperature is controlled at 50 DEG C, every time ultrasound extraction time 50min, and leaching liquor, each extraction are filtered by vacuum to obtain after extraction
Liquid merges, and vacuum freeze drying obtains willow bark tannin after Rotary Evaporators evaporate solvent.
Willow bark tannin is configured to the aqueous solution of 8% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 900W, quartz reaction kettle is placed under sunlight irradiation, then the tannin aqueous solution into reaction kettle
In tannin aqueous solution in be added mass fraction 6.5% (in terms of tannin quality) visible-light response type nano catalyst nano vanadic acid
Bismuth (BiVO4), then the hydrogen peroxide (H for accounting for tannin quality 50% is continuously added into tannin aqueous solution into reaction kettle2O2), dioxygen
The concentration of water is 50%, and every 1h is added 1 time, is being stirred, and reaction temperature controls under the conditions of 40 DEG C, carries out ultrasonic wave added visible light
Degradation reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 9h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.34, and the formaldehyde binding capacity before degradation is 0.42.
Embodiment 14
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the red hard wooden timber of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and aqueous acetone solution is 1:40, moistens the time 3.5h that rises every time, respectively extracts 1 under ultrasonic power 400W auxiliary
Secondary, extraction temperature is controlled at 60 DEG C, every time ultrasound extraction time 1h, and leaching liquor, each extraction are filtered by vacuum to obtain after extraction
Liquid merges, and vacuum freeze drying obtains the red hard wooden timber tannin after Rotary Evaporators evaporate solvent.
The red hard wooden timber tannin is configured to the aqueous solution of 11% concentration, is placed in supersonic generator, temperature controller
Quartz reaction kettle in, ultrasonic power 1100W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle
Mass fraction 7% (in terms of tannin quality) visible-light response type nano catalyst nano is added in tannin aqueous solution in aqueous solution
Ceria (CeO2), then the hydrogen peroxide (H for accounting for tannin quality 5% is continuously added into tannin aqueous solution into reaction kettle2O2),
The concentration of hydrogen peroxide is 30%, and every 1h is added 1 time, and under the conditions of reaction temperature is 50 DEG C, it is anti-to carry out ultrasonic wave added Visible Light Induced Photocatalytic
It answers；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 13h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.38, and the formaldehyde binding capacity before degradation is 0.66.
Embodiment 15
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the radix ephedrae of moisture content 12%, is ground into 100 with plant pulverizer
Purpose plant powder, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, plant powder with
The mixing ratio of aqueous acetone solution is 1:50, moistens the time 4h that rises every time, respectively extracts 1 time, extracts under ultrasonic power 150W auxiliary
Temperature is controlled at 70 DEG C, every time ultrasound extraction time 70min, and leaching liquor is filtered by vacuum to obtain after extraction, and each secondary leaching liquor closes
And vacuum freeze drying obtains radix ephedrae tannin after Rotary Evaporators evaporate solvent.
Radix ephedrae tannin is configured to the aqueous solution of 14% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 1300W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle is water-soluble
Mass fraction 7.5% (in terms of tannin quality) visible-light response type nano catalyst nano three is added in tannin aqueous solution in liquid
Tungsten oxide (WO3), then the hydrogen peroxide (H for accounting for tannin quality 50% is continuously added into tannin aqueous solution into reaction kettle2O2), it is double
The concentration of oxygen water is 50%, and every 1h is added 1 time, under the conditions of reaction temperature is 60 DEG C, carries out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 11h after formaldehyde binding capacity
No longer increase, stops degradation and be cooled to room temperature, obtain ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer aqueous solution, the water
Solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtains tannin polyphenol oligomer powder.The degradation product
Maximum formaldehyde binding capacity is 1.24, and the formaldehyde binding capacity before degradation is 0.51.
Embodiment 16
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the garden sorrel root of moisture content 11%, is ground into 110 with plant pulverizer
Purpose plant powder, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, plant powder with
The mixing ratio of aqueous acetone solution is 1:45, moistens the time 4.5h that rises every time, respectively extracts 1 time, soaks under ultrasonic power 250W auxiliary
Temperature raising degree is controlled at 80 DEG C, and ultrasound extraction time 80min, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains garden sorrel root tannin after Rotary Evaporators evaporate solvent.
Garden sorrel root tannin is configured to the aqueous solution of 17% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 1500W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle is water-soluble
The oxidation of (in terms of tannin quality) the visible-light response type nano catalyst nano of mass fraction 8% is added in tannin aqueous solution in liquid
Cuprous (Cu2O), the hydrogen peroxide (H for accounting for tannin quality 50% is continuously added into the tannin aqueous solution then into reaction kettle2O2), dioxygen
The concentration of water is 50%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 70 DEG C, and it is anti-to carry out ultrasonic wave added Visible Light Induced Photocatalytic
It answers；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 9h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.6
The maximum formaldehyde binding capacity of the degradation product is 1.28, and the formaldehyde binding capacity before degradation is 0.51.
Embodiment 17
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the treaster of moisture content 9%, is ground into 130 mesh with plant pulverizer
Plant powder, plant powder is sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, plant powder and first
The mixing ratio of alcohol solution is 1:55, moistens the time 2h that rises every time, is respectively extracted 1 time under ultrasonic power 350W auxiliary, extraction temperature
Degree control is at 55 DEG C, and ultrasound extraction time 0.5h, is filtered by vacuum to obtain leaching liquor every time after extraction, and each secondary leaching liquor merges,
Vacuum freeze drying obtains treaster tannin after Rotary Evaporators evaporate solvent.
Treaster tannin is configured to the aqueous solution of 19% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 1700W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle is water-soluble
Mass fraction 8.5% (in terms of tannin quality) visible-light response type nano catalyst nano iodine is added in tannin aqueous solution in liquid
Hydrogen peroxide (the H for accounting for tannin quality 40% is continuously added into bismuth oxide (BiOI), then tannin aqueous solution into reaction kettle2O2), it is double
The concentration of oxygen water is 40%, and every 1h is added 1 time, and reaction temperature controls under the conditions of 80 DEG C, carries out ultrasonic wave added Visible Light Induced Photocatalytic
Reaction；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 10h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 1.11, and the formaldehyde binding capacity before degradation is 0.47.
Embodiment 18
Over cleaning of learning from else's experience gets rid of impurity and gas is done to the dye yam stem tuber of moisture content 12%, is ground into plant pulverizer
The plant powder of 100 mesh, plant powder are sequentially placed into 50%, 60%, 70%, in the aqueous acetone solution of 80% concentration, Plant Powder
The mixing ratio of end and aqueous acetone solution is 1:25, moistens the time 5h that rises every time, respectively extracts 1 time under ultrasonic power 450W auxiliary,
Extraction temperature is controlled at 65 DEG C, and ultrasound extraction time 1.5h, is filtered by vacuum to obtain leaching liquor, each secondary leaching liquor every time after extraction
Merge, vacuum freeze drying obtains dye yam stem tuber tannin after Rotary Evaporators evaporate solvent.
Dye yam stem tuber tannin is configured to the aqueous solution of 5% concentration, is placed in the stone with supersonic generator, temperature controller
In English reaction kettle, ultrasonic power 1900W, quartz reaction kettle is placed under sunlight irradiation, then the tannin into reaction kettle is water-soluble
The vulcanization of (in terms of tannin quality) the visible-light response type nano catalyst nano of mass fraction 9% is added in tannin aqueous solution in liquid
Hydrogen peroxide (the H for accounting for tannin amount quality 35% is continuously added into cadmium (CdS), then tannin aqueous solution into reaction kettle2O2), dioxygen
The concentration of water is 35%, and every 1h is added 1 time, under the conditions of reaction temperature is 90 DEG C, carries out the reaction of ultrasonic wave added Visible Light Induced Photocatalytic；
In degradation process carry out formaldehyde association reaction, basic operation with embodiment 1, the difference is that: reaction 8h after first
Aldehyde binding capacity no longer increases, and stops degradation and is cooled to room temperature, obtains ultrasonic wave added Visible Light Induced Photocatalytic condensed tannin oligomer water
Solution, aqueous solution vacuum freeze drying after negative pressure Rotary Evaporators evaporate moisture content obtain tannin polyphenol oligomer powder.
The maximum formaldehyde binding capacity of the degradation product is 0.98, and the formaldehyde binding capacity before degradation is 0.32.
Claims (10)
1. a kind of ultrasonic wave added photocatalysis to selectively degradation condensed tannin and its palliating degradation degree control method, it is characterised in that:
The following steps are included:
Step 1) obtains condensed tannin from containing extraction in condensed tannin raw material；
Condensed tannin is configured to aqueous solution by step 2), and the aqueous solution is made to be condensed class under the conditions of ultrasonic wave added photocatalysis
Tannin is degraded, and interval time samples to obtain degradation solution；
Step 3) controls degradation step 2 using formaldehyde combined techniques) palliating degradation degree, to reacting for tannin and the formaldehyde in degradation solution
The reaction that step 2) is terminated when amount no longer increases, obtains condensed tannin oligomer aqueous solution.
2. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 1 and its palliating degradation degree controlling party
Method, it is characterised in that: the aqueous solution is placed under visible light or ultraviolet light prolonged exposure in the step 2), while to water-soluble
Liquid carries out ultrasound, then visible light or ultraviolet light response type catalyst are added into aqueous solution, and hydrogen peroxide, control reaction are added by several times
Temperature.
3. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 1 or 2 and its palliating degradation degree control
Method processed, it is characterised in that: the step 3) specific steps are as follows:
Sample of degrading 3-1) is divided into incipient degradation sample and processing degradation sample identical in quality, incipient degradation sample is dried to perseverance first
Weight, quality are denoted as M0；
Formalin 3-2) is added into processing degradation sample and hydrochloric acid solution obtains mixed solution, by mixed solution in oil bath item
It is heated to reflux under part, reacts tannin sufficiently with formaldehyde, and keep the leakproofness of reaction system；
3-3) after reaction, it after whole system is cooled to room temperature, filters, obtain solid product, solid product is placed in
It dries to constant weight in infrared baking oven, quality is denoted as M1, formaldehyde binding capacity F, calculation formula are as follows: F=(M are calculated according to formula1-M0)/
M0, stop degradation reaction when formaldehyde binding capacity F no longer increases.
4. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 3 and its palliating degradation degree controlling party
Method, it is characterised in that: the visible-light response type catalyst includes nano tungsten trioxide, nano cuprous oxide, nanometer iodine oxidation
One or more of bismuth, Nano cadmium sulphide, nano-copper sulfide, nanometer pucherite or nano ceric oxide；The ultraviolet light is rung
The type catalyst of answering includes nano-titanium dioxide, nanometer bismuth phosphate, nano-calcium carbonate silver, nano tin dioxide, nanometer α-di-iron trioxide
Or one or more of nano zine oxide.
5. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 4 and its palliating degradation degree controlling party
Method, it is characterised in that: in the step 2) mass concentration of aqueous solution be 2~20%, the ultrasonic power be 500~
2000W。
6. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 5 and its palliating degradation degree controlling party
Method, it is characterised in that: the addition quality of the photoresponse type catalyst is 0.5~9% of tannin quality in aqueous solution.
7. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 6 and its palliating degradation degree controlling party
Method, it is characterised in that: the step 2) hydrogen peroxide accounts for the 5~50% of tannin quality, and reaction temperature is controlled 20~100
DEG C, the concentration of hydrogen peroxide is 30~50%.
8. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 4 or 5 and its palliating degradation degree control
Method processed, it is characterised in that: the mass concentration of the formalin is 36.4~37.5%.
9. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 8 and its palliating degradation degree controlling party
Method, it is characterised in that: the step 1) specifically:
S1 the plant material that) will be enriched in condensed tannin is dry, is then comminuted into plant powder；
S2) plant powder is placed in a series of methanol/acetone aqueous solution of various concentrations, first by plant powder methanol/
Profit is carried out in aqueous acetone solution to rise；
S3 it) is successively extracted in the methanol/acetone aqueous solution under ultrasonic wave auxiliary in increasing concen-trations, extraction is successively filtered by vacuum to obtain
Liquid obtains condensed tannin through evaporation recycling design, vacuum freeze drying after merging leaching liquor.
10. ultrasonic wave added photocatalysis to selectively degradation condensed tannin according to claim 9 and its palliating degradation degree control
Method, it is characterised in that: the plant material rich in condensed tannin includes Black Wattle, yearning between lovers bark, bark of dahurian larch, short leaf
Pine bark, spruce bark, hemlock bark, red root bark, phyllanthus emblica bark, Chinese waxmyrtle bark, Albizzia kalkora bark, horse-tail bark, principal columns of a hall tree
One or more of bark, willow bark, the red hard wooden timber, radix ephedrae, garden sorrel root, treaster and dye yam stem tuber.
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