CN103724632A - Catalytic activation method of alkali lignin in black liquor by virtue of CuO/SO42-/ZrO2 - Google Patents
Catalytic activation method of alkali lignin in black liquor by virtue of CuO/SO42-/ZrO2 Download PDFInfo
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- CN103724632A CN103724632A CN201410003077.4A CN201410003077A CN103724632A CN 103724632 A CN103724632 A CN 103724632A CN 201410003077 A CN201410003077 A CN 201410003077A CN 103724632 A CN103724632 A CN 103724632A
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- alkali lignin
- lignin
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Abstract
The invention provides a catalytic activation method of alkali lignin in black liquor by virtue of CuO/SO42-/ZrO2. The method is used for extracting the alkali lignin from a black liquor dry matter and and improving the self chemical reactivity of alkali lignin. With the adoption of the method, a CuO/SO42-/ZrO2 catalyst is used to activate the alkali lignin purified from the black liquor dry matter in a hydrogen reduction system, the benzene ring structure of the activated alkali lignin is stable, the content of active functional groups is obviously increased, the total hydroxyl content is increased by 93.85 percent, the content of phenolic hydroxyl group is increased by 26.74 percent, and the content of alcoholic hydroxyl group is increased by 155.41 percent. The method provides a theoretical foundation for application technology study of lignin and also provides a new thought for resource real application of lignin.
Description
Technical field
The present invention is a kind of method of extracting and improve alkali lignin self chemical reactivity from the dry thing of black liquid.
Background technology
Xylogen is the abundant renewable organic resource of occurring in nature, and annual photosynthesis of plant can produce 50,000,000,000 tons of xylogen according to estimates, due to lignin molecule structure and aggregated structure complexity, the mankind to the research of application technique still in initial period.Alkali lignin is mainly derived from paper industry, annual production is about 1.5～1.8 hundred million tons, wherein most of as thermal source utilization, 1% (being mainly sulfonated lignin) of only having an appointment is reused as Organic chemistry sources, and a part is discharged in addition becomes pollutent in environment.Along with petrochemical industry resource is day by day exhausted and environmental pollution constantly aggravates, how to transform and utilize this natural polymer renewable resources of xylogen, of far-reaching significance to the mankind.
After the industrial treatment of high temperature, highly basic, there is complicated degraded and condensation reaction in alkali lignin, methoxy content is higher, and hydroxy radical content is lower, contains a large amount of Syringa oblata Lindl. bases and a small amount of guaiacyl, and chemical reactivity is low.Phenolic hydroxyl group and alcoholic extract hydroxyl group are functional group and the activation points of numerous lignin modification chemical reactions, improve alkali lignin phenolic hydroxyl group and alcoholic extract hydroxyl group content, strengthen alkali lignin chemical reactivity, are the basis of chemistry of lignin's reaction and the key of chemical modification.The people such as China Fang Guizhen develop Pd/C catalyzer, CuO/C catalyzer and the polyoxometallate α-K for alkali lignin activation
7[SiW
9cO
3(OH
2)
3o
37] catalyzer, successfully alkali lignin is activated, reduce alkali lignin methoxy content, improve the content of the total hydroxyl of alkali lignin, phenolic hydroxyl group and alcoholic extract hydroxyl group.
SO
4 2-/ ZrO
2to there is wide range of industrial applications prospect and environmentally friendly solid acid catalyst, polytype catalyzed reactions such as its energy efficient catalytic isomerization, cracking, esterification, CuO is conventional metal oxide catalyst.This research is with SO
4 2-/ ZrO
2solid acid is carrier, and metal oxide-loaded CuO, prepares CuO/SO
4 2-/ ZrO
2dual purpose catalyst, with H
2for reductive agent, the dioxane aqueous solution is solvent, in reactor, alkali lignin is activated, and uses total hydroxyl, phenolic hydroxyl group, alcoholic extract hydroxyl group active functional group content as index, investigates activation effect.After activation, alkali lignin benzene ring structure is stable, and active functional group content obviously improves, and total hydroxy radical content increases by 93.85%, and content of phenolic hydroxyl groups increases by 26.74%, and alcoholic extract hydroxyl group content increases by 155.41%.This activation method provides theoretical foundation for xylogen application technical research, simultaneously for Liginon Resource real world applications provides new approaches.
Summary of the invention
The present invention's alkali lignin of purifying from the dry thing of black liquid, is then used self-control CuO/SO
4 2-/ ZrO
2catalyzer activates alkali lignin in hydrogen reduction system.
Accompanying drawing explanation
The infrared spectrum of the forward and backward alkali lignin of observing response is known, wave number 1600cm
-1and 1506cm
-1place's aromatic ring vibrations are stable, and alkali lignin basic structure does not change, wave number 3410.57cm
-1place's hydroxyl O-H stretching vibration peak strengthens, wave number 1220.33cm
-1and 1030.92cm
-1the C-O stretching vibration peak of place's phenol and alcohol obviously strengthens, and total hydroxyl of alkali lignin is described, alcoholic extract hydroxyl group and content of phenolic hydroxyl groups increase, and alkali lignin activity increases.
Embodiment
Embodiment 1:
Purification alkali lignin: the dry thing of black liquid water-soluble (black liquid is dried thing: water=1: 9, mass ratio), filtering and impurity removing, filtrate adds certain density HCl to regulate pH=3, and suction filtration, is washed to neutrality by filter cake, drying under reduced pressure, grinds to form fine powder, makes alkali lignin.
Embodiment 2:
Kaolinite Preparation of Catalyst: by a certain amount of Zr (OH)
4impregnated in 1mol/L H
2sO
4middle 12h, 105 ℃ of dry 6h, 550 ℃ of roasting 3h make SO
4 2-/ ZrO
2solid acid catalyst, by SO
4 2-/ ZrO
2incipient impregnation in a certain amount of copper nitrate aqueous solution, drying under reduced pressure 24h, 350 ℃ of roasting 2h, make CuO/SO
4 2-/ ZrO
2catalyzer.
Embodiment 3:
React 1.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, does not add catalyzer, do not add H
2, in reactor, reaction conditions: 100 ℃ of temperature, time 4h, stirring velocity 400r/min.
Embodiment 4:
React 2.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, does not add catalyzer, pass into H
2in reactor, reaction conditions: 100 ℃ of temperature, time 4h, H
2pressure 3MPa, stirring velocity 400r/min.
Embodiment 5:
Reaction is 3.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, add 10% (catalyzer: xylogen=1: 10, mass ratio) SO
4 2-/ ZrO
2catalyzer, passes into H
2in reactor, reaction conditions: 100 ℃ of temperature, time 4h, H
2pressure 3MPa, stirring velocity 400r/min.
Embodiment 6:
Reaction is 4.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, add 5% (catalyzer: xylogen=1: 20, mass ratio) CuO/SO
4 2-/ ZrO
2catalyzer, passes into H
2in reactor, reaction conditions: 100 ℃ of temperature, time 4h, H
2pressure 3MPa, stirring velocity 400r/min.
Embodiment 7:
Reaction is 5.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, add 10% (catalyzer: xylogen=1: 10, mass ratio) CuO/SO
4 2-/ ZrO
2catalyzer, passes into H
2in reactor, reaction conditions: 100 ℃ of temperature, time 4h, H
2pressure 3MPa, stirring velocity 400r/min.
Embodiment 8:
Reaction is 6.: a certain amount of alkali lignin is dissolved in to the dioxane aqueous solution, add 20% (catalyzer: xylogen=1: 5, mass ratio) CuO/SO
4 2-/ ZrO
2catalyzer, passes into H
2in reactor, reaction conditions: 100 ℃ of temperature, time 4h, H
2pressure 3MPa, stirring velocity 400r/min.
Embodiment 9:
Alkali lignin after activating: reactant is filtered, separating catalyst, filtrate is concentrated in Rotary Evaporators, by concentrated solution drying under reduced pressure, grinds to form fine powder, makes the rear alkali lignin of activation.
Embodiment 10:
Alkali lignin FTIR detects: 2.0mg alkali lignin sample and 200mg Potassium Bromide are ground to rear compressing tablet, use FTIR-650 Fourier transform infrared spectrometer to measure, condition determination: wave number 1500-500cm
-1, resolving power 16cm
-1, scanning times 16.
Embodiment 11:
The total hydroxyl group determination of alkali lignin: adopt acetylize-hydrolysis method to measure total hydroxy radical content of alkali lignin.Accurately take 40mg alkali lignin in 10ml rub oral examination tube; add acetylation reagent (pyridine: diacetyl oxide: dioxane=4: 4.7: 4.4 with syringe; volume ratio) 0.6g; sealing; 50 ℃ of isothermal reaction 24h; after reaction finishes; add 5ml acetone; wash constant volume in 25ml volumetric flask with the mixing solutions (dioxane: water, 4: 1, volume ratio) of dioxane and water; get 5ml solution; phenolphthalein is indicator, with the titration of 0.1mol/L standard solution of sodium hydroxide, obtains total hydroxy radical content after calculating.
Embodiment 12:
Alkali lignin phenolic hydroxyl group is measured: the content of phenolic hydroxyl groups that adopts Differential Spectrophotometry for Determining alkali lignin.Take 10mg alkali lignin, add mixing solutions (dioxane: water, 4: 1, volume ratio) constant volume in 25ml volumetric flask of dioxane and water.Get 1ml alkali lignin, dioxane, the aqueous solution and add potassium primary phosphate, the sodium hydroxide buffer solution of pH=6 to be surely dissolved in 25ml volumetric flask, as the blank of measuring absorbancy.Get 1ml lignin, dioxane, the aqueous solution and add 0.2mol/L sodium hydroxide solution to be surely dissolved in 25ml volumetric flask, at 300nm and 360nm wavelength place, measure absorbance, after calculating, obtain total hydroxy radical content.
Embodiment 13:
Alkali lignin alcoholic extract hydroxyl group is measured: by the difference indirect measurement of total hydroxyl and phenolic hydroxyl group, obtain alcoholic extract hydroxyl group content after calculating.
Claims (1)
1. with the 4-dioxane aqueous solution, dissolve alkali lignin, use self-control CuO/SO
4 2-/ZrO
2catalyzer, H
2, in reactor, alkali lignin being activated, reaction conditions is, alkali lignin consumption 1-10g, catalyzer add-on 0.1-2.0g, temperature 60-120 ℃, H
2pressure 1-5MPa, stirring velocity 200-800r/min, time 2-6h, by catalyst separating, by concentrated reaction solution, dry, obtains activating rear alkali lignin after reaction finishes.
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| CN201410003077.4A CN103724632B (en) | 2014-01-03 | 2014-01-03 | CuO/SO 42-/ ZrO 2the method of alkali lignin in catalytic activation black liquid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910341A (en) * | 2015-06-24 | 2015-09-16 | 湖南师范大学 | Method for preparing lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO |
| CN105542190A (en) * | 2015-10-27 | 2016-05-04 | 东北林业大学 | Method for catalytic activation of alkali lignin by Pd/SO4<2->/ZrO2 |
| CN106853374A (en) * | 2016-12-13 | 2017-06-16 | 徐州诺克非医药科技有限公司 | A kind of 2,6 2 benzal pentylcyclohexanone synthesis techniques as medicine and pesticide intermediate |
| CN109467716A (en) * | 2018-11-06 | 2019-03-15 | 安徽理工大学 | A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin |
| CN110105588A (en) * | 2019-06-11 | 2019-08-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of novel sulfonated lignin |
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| WO2000011112A1 (en) * | 1998-08-21 | 2000-03-02 | The University Of Utah Research Foundation | Process for conversion of lignin to reformulated, partially oxygenated gasoline |
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2014
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Patent Citations (4)
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| WO2000011112A1 (en) * | 1998-08-21 | 2000-03-02 | The University Of Utah Research Foundation | Process for conversion of lignin to reformulated, partially oxygenated gasoline |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910341A (en) * | 2015-06-24 | 2015-09-16 | 湖南师范大学 | Method for preparing lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO |
| CN105542190A (en) * | 2015-10-27 | 2016-05-04 | 东北林业大学 | Method for catalytic activation of alkali lignin by Pd/SO4<2->/ZrO2 |
| CN106853374A (en) * | 2016-12-13 | 2017-06-16 | 徐州诺克非医药科技有限公司 | A kind of 2,6 2 benzal pentylcyclohexanone synthesis techniques as medicine and pesticide intermediate |
| CN106853374B (en) * | 2016-12-13 | 2019-04-30 | 甘肃泰升化工科技有限公司 | A kind of bis- benzal pentylcyclohexanone synthesis technology of 2,6- as medicine and pesticide intermediate |
| CN109467716A (en) * | 2018-11-06 | 2019-03-15 | 安徽理工大学 | A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin |
| CN110105588A (en) * | 2019-06-11 | 2019-08-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of novel sulfonated lignin |
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