CN102277591A - Method for electrochemically degrading lignin - Google Patents
Method for electrochemically degrading lignin Download PDFInfo
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- CN102277591A CN102277591A CN2011102192093A CN201110219209A CN102277591A CN 102277591 A CN102277591 A CN 102277591A CN 2011102192093 A CN2011102192093 A CN 2011102192093A CN 201110219209 A CN201110219209 A CN 201110219209A CN 102277591 A CN102277591 A CN 102277591A
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- lignin
- xylogen
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Abstract
The invention relates to a method for electrochemically degrading lignin. A cathode and an anode of an electrolytic cell used by the method are arranged in parallel at short distance in an inclined manner, the cathode is on top, the cathode is on bottom, and oxygen generated by the anode is restored into hydrogen peroxide on the cathode. Newly generated hydrogen peroxide has oxidative degradation action on lignin, active hydrogen generated on the cathode can restore oxygenated radicals in oxidative cracked fragments into hydroxide radicals, and lignin degradation products with small molecular weight and more hydroxide radicals are finally obtained.
Description
Technical field
The invention belongs to the field of xylogen utilization of resources, relate to a kind of electrochemistry depolymerization xylogen, reduce its molecular weight, improve xylogen hydroxyl value and reactive behavior, make it to become and partly to substitute the technological method of polyether glycol in order to the production polyurethane material.
Technical background
Xylogen is only second to cellulosic second largest natural organic high-molecular compound as occurring in nature on total amount, be one of important renewable resources.Xylogen is the main by product of paper industry, at present, pulping waste liquor xylogen above 95% is still as waste, with waste water directly enter rivers or concentrate after burn, this not only causes the huge waste of resource, while is contaminate environment again, therefore, how to realize that the recycling of xylogen more and more is subject to people's attention.
Xylogen is the randomness Polyphenols macromolecular compound that is formed by connecting by ehter bond and C-C key by phenylpropyl alcohol alkyl structure unit (C9), and wherein the mode with ehter bond connects more than 50%.Because lignin molecule amount big (3000-10000 dalton), reactive behavior are low, thereby utilization ratio is low.For realizing the xylogen utilization of resources, need carry out degradation modification to it, its molecular weight reduction, activity hydroxy number are increased, xylogen after the degraded can replace or part replaces polyether glycol to be used for synthesis of polyurethane, thereby realizes utilization of resources, improves environment, development national economy.
At present, the method that xylogen is degraded mainly contains chemical oxidation cracking process, shortening cracking, advanced oxidation degradation and biological degradation.The chemical oxidation cracking mainly is to utilize oil of mirbane, ozone, clorox, ClO
2, oxygenant such as sodium chlorate comes the chemical bond in the oxidation scission lignin molecule.But use oxygenant and can produce some problems: big as reagent price height, consumption, can't reclaim, itself also has toxicity etc. part reagent.The shortening cracking is to make C-C in the lignin molecule because hydrogenation and scission of link, and wherein used catalyzer is noble metal catalyst mostly, costs an arm and a leg, is difficult to reclaim, and need high pressure reactor.The advanced oxidation mode mainly is to utilize Fenton reagent (H
2O
2+ Fe
2+), oxidation means lignin degrading such as photochemical catalysis, plasma body, degradation effect is fine, but can't realize serialization production.
Summary of the invention
The present invention proposes a kind of method of electrochemical means lignin degrading, specifically, preferably transform into hydrogen peroxide in the cathodic reduction close by electrode materials exactly with it with the oxygen that the optimization design of electrode lay-out generates anode, and hydrogen peroxide its play the effect of appropriate oxidative degradation xylogen.
The oxygen that principle of the present invention is based on the anode generation is reduced the reaction that generates hydrogen peroxide on the surface of negative electrode, reaction formula is 2H
2O+O
2+ 2e=H
2O
2+ 2OH
-, the reaction of oxidation depolymerization takes place in xylogen under the hydrogen peroxide effect thereupon.By with negative electrode and anode with closely parallel and be in tilted layout, make the oxygen that generates at anode in uphill process, the chance that fully contacts be arranged with negative electrode, promote it to be converted into, improve the efficient of electrochemistry depolymerization xylogen greatly interrupting highly effective hydrogen peroxide such as xylogen β-O-4 ehter bond and alkyl group side chain.
In addition, the activity [H] that also has status nascendi on the negative electrode produces, and it has stronger reducing power, can make the more weak β-O-4 ehter bond generation reduction fracture of chemical bond in the xylogen on the one hand, produces phenolic hydroxyl group and alcoholic extract hydroxyl group, on the other hand can be with H
2O
2The carbonyl reduction that oxidation produced is an alcoholic extract hydroxyl group, and the hydroxy radical content of xylogen is further increased.
Because H
2O
2Oxidation and the reduction of status nascendi active hydrogen [H] have opposite effect, may weaken mutually under certain conditions.Characteristics of the present invention are to regulate and control the degree of reaction by controlling certain pH value, flow velocity, electrolysis temperature and current density, thereby make the xylogen macromole by H
2O
2Oxidation scission and nascent hydrogen [H] reduce the two effect and can both give full play to, and the lignin molecule amount is reduced, and hydroxy radical content increases, and improves the segmental reactive behavior of lignin depolymerization.
When xylogen was carried out the depolymerization modification, the repolymerization reaction took place in the xylogen small molecule segment of depolymerization easily, and electrochemical degradation efficient is reduced, and added a small amount of stopper phenol or Resorcinol or ethanol for this reason, to stop the segmental repolymerization of depolymerization.It mainly is because they are oxidized to benzoquinones easily that phenol or Resorcinol can play inhibition, and benzoquinones can play the seizure effect to the free radical that cracking generates, and makes coupling or disproportionation termination, prevents the combination between the free radical, thereby reaches inhibition; It mainly is because the combined with radical that it can generate with cracking plays certain stable provide protection that ethanol can play inhibition, prevents the repolymerization of free radical, plays inhibition.
Cell construction synoptic diagram that the electrochemical redox depolymerization xylogen method that the present invention proposes is used and electrolyzer synoptic diagram are referring to accompanying drawing.The inclined closely parallel placement of battery lead plate, the angle of inclination is between the 10-80 degree, and interpole gap is controlled between 10～15mm, and on vertical direction, anode is following, and negative electrode is last, with the O that guarantees that anode produces
2Arrive negative electrode during come-up rapidly, and rise, fully contact, improve current efficiency greatly with negative electrode along cathode surface.Anode and cathode can multilayer alternately be placed, be not limited to only draw in the accompanying drawing 1 two-layer, the feed liquor divider that electrolytic solution is formed from the cone tank and the orifice plate of device lower end enters, flow velocity by control liquid-inlet pipe liquid can keep electrolysis system uniform and stable, especially for heterogeneous electrolysis system, the feed liquor divider can avoid solid particulate to residue in " dead angle ", helps the xylogen solid granulates and suspends mobile, stabilizing technical processes improves electrolysis depolymerization efficient; The flow velocity of xylogen electrolytic solution is regulated by pump valve, and the temperature of electrolytic solution is regulated by heat exchanger heats, and Faradaic current is controlled by power regulator, and electrolysis time requires to decide on the particular case and the depolymerization of electrolysis material, referring to accompanying drawing 2.
Electrochemical appliance of the present invention can carry out the continuous flow electrolysis or circulate electrolysis or non-current static electrolysis the xylogen aqueous solution.
The anode of electrochemical appliance of the present invention, its material can be resistant metal or alloys such as ti-supported lead dioxide electric, titanium ruthenium, titanium ruthenium iridium, nickel, nickel foam.
The negative electrode of electrochemical appliance of the present invention, its material can be graphite cake, the graphite felt through the fixing processing of anti-short circuit, copper, foam copper, stainless steel, nickel foam etc.
The electrolysis process condition: the xylogen concentration of aqueous solution is 1%-20% (mass ratio), and the addition of stopper is the 0.5%-10% (mass ratio) of content of lignin in the solution, and the pH value of solution is controlled at 3-12; Current density is 1-10mA/cm in the electrolytic process
2, electrolysis temperature is controlled at 20-90 ℃, and liquid flow rate is 0-600ml/min.
The present invention adopts water as electrolytic solvent, and low price is pollution-free.Compare without catalyzer with other chemical degradation method, avoided catalyst residue in lignin product, so lignin product purity height, be more suitable for substituting polyether glycol as raw material production urethane; With the Direct Electrochemistry oxidation style than having the high characteristics of electrolytic efficiency because can be with the generation of oxygen evolution reaction in the electrochemical reaction, and the present invention have utilized the O that separates out fully
2Produce H in cathodic reduction
2O
2Come oxidation depolymerization xylogen.
Device of the present invention is not only applicable to the homogeneous reaction system of degradation treatment xylogen, also be applicable to the heterogeneous suspension system of solid lignin and lignin liquor coexistence simultaneously, and entire reaction course is easy to regulation and control, can be by the different condition of control, reach different modified effects to xylogen, handling good, suitability is strong.
Novelty of the present invention also is to have added stopper phenol or Resorcinol or ethanol in electrolytic solution.Phenol or Resorcinol can transform the mode Mulberry Extract of benzoquinones or diquinone by part when carrying out electrolysis, to prevent to have the xylogen fragment repolymerization of free radical, ethanol can play stable deactivation to free radical, it can stop the xylogen small molecules fragment after the degraded that polymerization takes place once more, thereby has increased electrochemical degradation efficiency.
Equipment used in the present invention is simple, and cost is lower, can reduce the pollution to environment significantly, and reaction process controls easily, is easy to realize that continous way in enormous quantities handles xylogen, is suitable for suitability for industrialized production.
Description of drawings
The cell construction synoptic diagram of accompanying drawing 1. electrochemical degradation xylogen
The 1-orifice plate
The 2-negative electrode
The 3-anode
The 4-drain pipe
5-feed liquor divider
The 6-liquid-inlet pipe
The device synoptic diagram of accompanying drawing 2. electrochemical degradation xylogen
But 1-voltage controller power source
The 2-pump
The 3-valve
4-raw material (or product) storage tank
The 5-under meter
The 6-interchanger
The 7-electrolyzer
The 8-sampling valve
9-product storage tank
Embodiment
Embodiment 1
Be 10cm long, wide is 10cm, and thick is in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, and the anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, makes anode with titanium ruthenium net, makes negative electrode with graphite cake, circulates electrolysis after the injection straw lignin heterogeneous solution.The concentration of maize straw enzymolysis xylogen solution is 6%, and stopper phenol amount of filling is 5% of an xylogen quality, the pH=4 of solution, and control current density is 3mA/cm in the electrolytic process
2, (about 25 ℃) electrolysis at room temperature, flow of electrolyte is 400ml/min, electrolysis time is 2h.Electrolysis finishes after extraction, drying and other steps obtain product.The weight-average molecular weight of degraded back xylogen has reduced by 69.1% than the log quality, and polydispersity coefficient is reduced to 1.743 by original 3.520, and hydroxyl value is increased to present 389mgKOH/g by the 217mgKOH/g of log quality, has increased by 79.3%.
Be 10cm long, wide be 10cm, and thick be in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, and is and replaces placement, and the anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, makes anode with the ti-supported lead dioxide electric net, does negative electrode with nickel foam, injects the non-current static electrolysis of the laggard row of purifying lignosulfonic acid salts solution.The concentration of purifying lignosulfonic acid salts solution is 15%, and stopper ethanol amount of filling is 10% of an xylogen quality, the pH=12 of solution, and control current density is at 10mA/cm in the electrolytic process
2, electrolysis temperature is controlled at 70 ℃, and flow of electrolyte is 0ml/min, and electrolysis time is 2h.The electrolysis end is after acid precipitation, extraction, drying and other steps obtain product.The weight-average molecular weight of degraded back xylogen has reduced by 55.4% than the log quality, and polydispersity coefficient is reduced to 1.619 by original 2.558, and hydroxyl value is increased to present 315mgKOH/g by the 199mgKOH/g of log quality, has increased by 58.3%.
Be 10cm long, wide is 10cm, and thick is in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, and the anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, makes anode with titanium ruthenium net, makes negative electrode with foam copper, carries out continuous electrolysis behind the injection purifying alkali lignin solution.The concentration of purifying alkali lignin solution is 5%, and stopper phenol amount of filling is 5% of an xylogen quality, the pH=11 of solution, and control current density is at 4mA/cm in the electrolytic process
2, electrolysis temperature is controlled at 40 ℃, and flow of electrolyte is 20ml/min, and the electrolysis end is after acid precipitation, extraction, drying and other steps obtain product.The weight-average molecular weight of degraded back xylogen has reduced by 71.6% than the log quality, and polydispersity coefficient is reduced to 1.366 by original 2.989, and hydroxyl value is increased to present 249mgKOH/g by the 137mgKOH/g of log quality, has increased by 81.7%.
Be 10cm long, wide is 10cm, and thick is in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, and the anode and cathode area is 10 * 10cm
2, interpole gap is 1.5cm, makes anode with titanium ruthenium iridium net, makes negative electrode with graphite felt, places the rigid plastics net and play fixedly the graphite felt electrode and prevent short circuit between the two poles of the earth, carries out continuous electrolysis behind the injection straw lignin solution.The concentration of maize straw enzymolysis xylogen solution is 2%, and the hydroquinone of polymerization retarder amount of filling is 1% of an xylogen quality, the pH=10 of solution, and control current density is at 2mA/cm in the electrolytic process
2, (about 25 ℃) electrolysis at room temperature, flow of electrolyte is 10ml/min.The electrolysis end is after acid precipitation, extraction, drying and other steps obtain product.The weight-average molecular weight of degraded back xylogen has reduced by 76.4% than the log quality, and polydispersity coefficient is reduced to 1.265 by original 3.520, and hydroxyl value is increased to present 454mgKOH/g by the 217mgKOH/g of log quality, has increased by 109.2%.
Claims (6)
1. an electrochemical means is degraded and is gathered the method for xylogen, the cathode and anode that it is characterized in that the electrolyzer that uses is skewed closely parallel placement, interpole gap is no more than 15mm, the oxygen that anode produces is reduced to hydrogen peroxide at cathode surface, xylogen in the electrolytic solution is produced the effect of oxidation scission of link, molecular weight is reduced; The active hydrogen of negative electrode generation simultaneously increases hydroxy radical content to the reduction of the oxidisability group in the xylogen fragment.
2. the method for electrochemical means lignin degrading as claimed in claim 1, wherein the anode material can be ti-supported lead dioxide electric, titanium ruthenium, titanium ruthenium iridium, nickel, nickel foam in the electrochemical appliance; The negative electrode material can be graphite cake, fix graphite felt, copper, foam copper, stainless steel, the nickel foam of handling through anti-short circuit.
3. the method for electrochemical means lignin degrading as claimed in claim 1, wherein the xylogen concentration of aqueous solution is 1%-20% (mass ratio), and the pH value is between 3-12, and the stopper addition is the 0.5%-10% (mass ratio) of xylogen in the solution; Current density is 1-10mA/cm in the electrolytic process
2, electrolysis temperature is controlled at 20-90 ℃, and liquid flow rate is 0-600ml/min.
4. the method for electrochemical means lignin degrading as claimed in claim 1 is characterized in that used xylogen can be alkali lignin, straw lignin, sulfonated lignin, high-boiling alcohol lignin.
5. the method for electrochemical means lignin degrading as claimed in claim 1 is characterized in that being used for the nonhomogeneous system that degradation treatment lignin liquor or solid lignin and lignin liquor coexist.
6. the method for electrochemical means lignin degrading as claimed in claim 1, wherein stopper is phenol, ethanol or Resorcinol.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074639A (en) * | 2013-02-04 | 2013-05-01 | 河北工业大学 | Method for preparing 2, 6-ditertiary butyl-4-methylphenol by electrochemically degrading lignin |
| CN104062332A (en) * | 2014-06-30 | 2014-09-24 | 浙江天能电池(江苏)有限公司 | Determination method for lignosulfonic acid sodium salt capacity for resisting to electrochemical oxidation |
| CN106045141A (en) * | 2016-06-30 | 2016-10-26 | 浙江大学苏州工业技术研究院 | Method and device for electrochemical treatment of medical and chemical wastewater |
| CN106480472A (en) * | 2015-08-25 | 2017-03-08 | 中国科学院天津工业生物技术研究所 | Biological material one step is converted into method, container and the purposes of solable matter |
| CN106661742A (en) * | 2014-07-25 | 2017-05-10 | 夏普株式会社 | Electrolysis device |
| CN106676574A (en) * | 2017-01-22 | 2017-05-17 | 河北工业大学 | Method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through electro-catalysis technology |
| CN106868862A (en) * | 2017-03-21 | 2017-06-20 | 张辰龙 | A kind of preparation method of degree of spinning antistatic hemp high |
| CN109518209A (en) * | 2019-01-15 | 2019-03-26 | 河北工业大学 | The method that 4-hydroxyanisol unit and tertiary butyl chloride in electro-catalysis lignin prepare 3- tert-butyl 4-hydroxyanisol |
| CN109680296A (en) * | 2018-12-24 | 2019-04-26 | 河北工业大学 | A method of the O-methoxy phenolic group group decomposited with lignin prepares eugenol with additional allyl reaction |
| CN112094304A (en) * | 2020-09-19 | 2020-12-18 | 周静 | Separation and purification method of enzymatic hydrolysis lignin |
| CN112831799A (en) * | 2020-12-30 | 2021-05-25 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| WO2021257972A1 (en) | 2020-06-18 | 2021-12-23 | Texas Tech University System | Processes for electrochemical up-cycling of plastics and systems thereof |
| CN115521479A (en) * | 2022-09-15 | 2022-12-27 | 上海应用技术大学 | Preparation method of lignin derivative |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074639B (en) * | 2013-02-04 | 2015-04-29 | 河北工业大学 | Method for preparing 2, 6-ditertiary butyl-4-methylphenol by electrochemically degrading lignin |
| CN103074639A (en) * | 2013-02-04 | 2013-05-01 | 河北工业大学 | Method for preparing 2, 6-ditertiary butyl-4-methylphenol by electrochemically degrading lignin |
| CN104062332A (en) * | 2014-06-30 | 2014-09-24 | 浙江天能电池(江苏)有限公司 | Determination method for lignosulfonic acid sodium salt capacity for resisting to electrochemical oxidation |
| CN106661742A (en) * | 2014-07-25 | 2017-05-10 | 夏普株式会社 | Electrolysis device |
| CN106480472B (en) * | 2015-08-25 | 2019-03-12 | 中国科学院天津工业生物技术研究所 | Convert one step of biological material to method, container and the purposes of solable matter |
| CN106480472A (en) * | 2015-08-25 | 2017-03-08 | 中国科学院天津工业生物技术研究所 | Biological material one step is converted into method, container and the purposes of solable matter |
| CN106045141A (en) * | 2016-06-30 | 2016-10-26 | 浙江大学苏州工业技术研究院 | Method and device for electrochemical treatment of medical and chemical wastewater |
| CN106676574A (en) * | 2017-01-22 | 2017-05-17 | 河北工业大学 | Method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through electro-catalysis technology |
| CN106868862A (en) * | 2017-03-21 | 2017-06-20 | 张辰龙 | A kind of preparation method of degree of spinning antistatic hemp high |
| CN109680296A (en) * | 2018-12-24 | 2019-04-26 | 河北工业大学 | A method of the O-methoxy phenolic group group decomposited with lignin prepares eugenol with additional allyl reaction |
| CN109518209A (en) * | 2019-01-15 | 2019-03-26 | 河北工业大学 | The method that 4-hydroxyanisol unit and tertiary butyl chloride in electro-catalysis lignin prepare 3- tert-butyl 4-hydroxyanisol |
| CN109518209B (en) * | 2019-01-15 | 2020-08-25 | 河北工业大学 | Method for preparing 3-tert-butyl 4-hydroxyanisole by electrocatalysis of 4-hydroxyanisole unit and tert-butyl chloride in lignin |
| WO2021257972A1 (en) | 2020-06-18 | 2021-12-23 | Texas Tech University System | Processes for electrochemical up-cycling of plastics and systems thereof |
| CN112094304A (en) * | 2020-09-19 | 2020-12-18 | 周静 | Separation and purification method of enzymatic hydrolysis lignin |
| CN112831799A (en) * | 2020-12-30 | 2021-05-25 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| CN112831799B (en) * | 2020-12-30 | 2022-12-23 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| CN115521479A (en) * | 2022-09-15 | 2022-12-27 | 上海应用技术大学 | Preparation method of lignin derivative |
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