CN102277591B - Method for electrochemically degrading lignin - Google Patents
Method for electrochemically degrading lignin Download PDFInfo
- Publication number
- CN102277591B CN102277591B CN201110219209.3A CN201110219209A CN102277591B CN 102277591 B CN102277591 B CN 102277591B CN 201110219209 A CN201110219209 A CN 201110219209A CN 102277591 B CN102277591 B CN 102277591B
- Authority
- CN
- China
- Prior art keywords
- lignin
- xylogen
- anode
- cathode
- electrochemical means
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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 field that the invention belongs to the effective utilization of Liginon Resource, relates to a kind of electrochemistry depolymerization xylogen, reduces its molecular weight, improves xylogen hydroxyl value and reactive behavior, makes it to become can partly substitute polyether glycol in order to produce the technological method of polyurethane material.
Technical background
Xylogen is only second to cellulosic second largest natural organic high-molecular compound in total amount as occurring in nature, be one of important renewable resources.Xylogen is the Main By product of paper industry, at present, Lignin from Pulping Spent Liquor over 95% is still as waste, with waste water directly enter rivers or concentrated after burn, this not only causes the huge waste of resource, while is contaminate environment again, and therefore, recycling how to realize xylogen is more and more subject to people's attention.
Xylogen is the randomness Polyphenols macromolecular compound being formed by connecting by ehter bond and C-C key by phenylpropyl alcohol alkyl structure unit (C9), and wherein more than 50% the mode with ehter bond connects.Because lignin molecule amount large (3000-10000 dalton), reactive behavior are low, thereby utilization ratio is low.For realizing Liginon Resource, effectively utilize, need to carry out degradation modification to it, its molecular weight reduction, activity hydroxy number are increased, xylogen after degraded can replace or part replaces polyether glycol for the synthesis of urethane, thereby realizes utilization of resources, improves environment, developing national economy.
The method of at present, xylogen being degraded mainly contains chemical oxidation cracking process, shortening cracking, advanced oxidation degradation and biological degradation.Chemical oxidation cracking is mainly to utilize oil of mirbane, ozone, clorox, ClO
2, the oxygenant such as sodium chlorate carrys out the chemical bond in oxidation scission lignin molecule.But application oxygenant can produce some problems: as high in reagent price, consumption is large, cannot reclaim, itself also has toxicity etc. part reagent.Shortening cracking be make C-C in lignin molecule due to hydrogenation scission of link, wherein catalyzer used is noble metal catalyst mostly, expensive, be difficult to reclaim, and needs high pressure reactor.Advanced oxidation mode is mainly to utilize Fenton reagent (H
2o
2+ Fe
2+), the oxidation means lignin degrading such as photochemical catalysis, plasma body, degradation effect is fine, but cannot realize serialization, produces.
Summary of the invention
The present invention proposes a kind of method of electrochemical means lignin degrading, specifically, by electrode materials, preferably in the cathodic reduction close with it, transform into hydrogen peroxide with the oxygen that the optimization design of electrode lay-out generates anode exactly, and hydrogen peroxide its play the effect of appropriate oxidative degradation xylogen.
Principle of the present invention is that the oxygen producing based on anode is reduced the reaction of Hydrogen Peroxide on the surface of negative electrode, and reaction formula is 2H
2o+O
2+ 2e=H
2o
2+ 2OH
-, there is the reaction of oxidative degradation in xylogen thereupon under hydrogen peroxide effect.By by negative electrode and anode with closely parallel and be in tilted layout, make the oxygen generating at anode have with negative electrode the chance fully contacting in uphill process, promote it to be converted into interrupting the highly effective hydrogen peroxide such as xylogen β-O-4 ehter bond and alkyl group side chain, greatly improve the efficiency of electrochemistry depolymerization xylogen.
In addition, the activity [H] that also has status nascendi on negative electrode produces, and it has stronger reducing power, can make on the one hand the weak β-O-4 ehter bond generation reduction fracture of chemical bond in xylogen, produces phenolic hydroxyl group and alcoholic extract hydroxyl group, on the other hand can be by H
2o
2the carbonyl reduction that oxidation produces is alcoholic extract hydroxyl group, and the hydroxy radical content of xylogen is further increased.
Due to H
2o
2oxidation and the reduction of status nascendi active hydrogen [H] there is opposite effect, may weaken mutually under certain conditions.Feature of the present invention is to regulate and control the degree of reaction by controlling certain pH value, flow velocity, electrolysis temperature and current density, thereby makes xylogen macromole by H
2o
2oxidation scission and nascent hydrogen [H] reduce the two effect and can give full play to, and lignin molecule amount is reduced, and hydroxy radical content increases, and improves the reactive behavior of lignin depolymerization fragment.
When xylogen is carried out to depolymerization modification, easily there is repolymerization reaction in the xylogen small molecule segment of depolymerization, makes electrochemical degradation Efficiency Decreasing, adds a small amount of stopper phenol or Resorcinol or ethanol, to stop the repolymerization of depolymerization fragment for this reason.It is mainly because they are easily oxidized to benzoquinones that phenol or Resorcinol can play inhibition, and the free radical that benzoquinones can generate cracking plays seizure effect, makes coupling or disproportionation termination, prevents the combination between free radical, thereby reaches inhibition; It is mainly the combined with radical that can generate with cracking due to it that ethanol can play inhibition, plays certain stable provide protection, prevents the repolymerization of free radical, plays inhibition.
The cell construction schematic diagram that electrochemical redox depolymerization xylogen method that the present invention proposes is used and electrolyzer schematic diagram are referring to accompanying drawing.The inclined closely parallel placement of battery lead plate, angle of inclination is between 10-80 degree, interpole gap is controlled between 10～15mm, from Vertical Square, look up, anode under, negative electrode is upper, with the O that guarantees that anode produces
2during floating, arrive rapidly negative electrode, and rise along cathode surface, fully contact with negative electrode, greatly improve current efficiency.Anode and cathode can multilayer alternately be placed, be not limited to only draw in accompanying drawing 1 two-layer, electrolytic solution enters from the cone tank of device lower end and the feed liquor divider of orifice plate composition, by controlling the flow velocity of liquid-inlet pipe liquid, can keep electrolysis system uniform and stable, especially for heterogeneous electrolysis system, feed liquor divider can avoid solid particulate to residue in " dead angle ", is conducive to xylogen solid granulates and suspends mobile, stabilizing technical processes, improves electrolysis depolymerization efficiency; The flow velocity of xylogen electrolytic solution regulates by pump valve, and the temperature of electrolytic solution regulates by heat exchanger heats, and Faradaic current is controlled by power regulator, and electrolysis time requires depending on particular case and the depolymerization of electrolysis material, referring to accompanying drawing 2.
Electrochemical appliance of the present invention can carry out 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 the 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.
Electrolytic conditions: xylogen concentration of aqueous solution is 1%-20% (mass ratio), the addition of stopper is the 0.5%-10% (mass ratio) of content of lignin in solution, the pH value of solution is controlled at 3-12; In electrolytic process, current density is 1-10mA/cm
2, electrolysis temperature is controlled at 20-90 ℃, and liquid flow rate is 0-600ml/min.
The present invention adopts water as the solvent of electrolysis, and low price is pollution-free.Compare without catalyzer with other chemical degradation method, avoided catalyst residue in lignin product, so lignin product purity is high, be more suitable for substituting polyether glycol as raw material production urethane; Than having the advantages that electrolytic efficiency is high, because meeting is with the generation of oxygen evolution reaction in electrochemical reaction, and the present invention has utilized the O separating out fully with Direct Electrochemistry oxidation style
2in cathodic reduction, produce H
2o
2carry out oxidative degradation 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 that solid lignin and lignin liquor coexist simultaneously, and whole reaction process is easy to regulation and control, can be by controlling different conditions, reach the different modified effects to xylogen, handling good, suitability is strong.
Novelty of the present invention is also to have added stopper phenol or Resorcinol or ethanol in electrolytic solution.When carrying out electrolysis, phenol or Resorcinol can be by the mode Mulberry Extracts of Partial Conversion benzoquinones or diquinone, to prevent the xylogen fragment repolymerization with free radical, ethanol can play stable deactivation to free radical, it can stop the xylogen small molecules fragment after degraded that polymerization occurs again, thereby has increased electrochemical degradation efficiency.
Equipment used in the present invention is simple, and cost is lower, can significantly reduce the pollution to environment, and reaction process easily controls, and is easy to realize continous way in enormous quantities and processes xylogen, is suitable for suitability for industrialized production.
Accompanying drawing explanation
The cell construction schematic diagram of accompanying drawing 1. electrochemical degradation xylogen
1-orifice plate
2-negative electrode
3-anode
4-drain pipe
5-feed liquor divider
6-liquid-inlet pipe
The device schematic diagram of accompanying drawing 2. electrochemical degradation xylogen
1-pressure-adjustable power supply
2-pump
3-valve
4-raw material (or product) storage tank
5-under meter
6-interchanger
7-electrolyzer
8-sampling valve
9-product storage tank
Embodiment
Embodiment 1
Long be 10cm, wide is 10cm, thick is, in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, with titanium ruthenium net, makes anode, with graphite cake, makes negative electrode, after injection straw lignin heterogeneous solution, circulates electrolysis.The concentration of maize straw enzymolysis xylogen solution is 6%, and stopper phenol amount of filling is 5% of xylogen quality, the pH=4 of solution, and in electrolytic process, controlling current density is 3mA/cm
2, at room temperature (25 ℃ of left and right) electrolysis, flow of electrolyte is 400ml/min, electrolysis time is 2h.Electrolysis finishes to obtain product by extraction, drying and other steps.After degraded, the weight-average molecular weight of xylogen has reduced by 69.1% compared with 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%.
Embodiment 2
Long be 10cm, wide be 10cm, thick be, in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, and is and replaces placement, anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, with ti-supported lead dioxide electric net, makes anode, with nickel foam, does negative electrode, 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 xylogen quality, and the pH=12 of solution controls current density at 10mA/cm in electrolytic process
2, electrolysis temperature is controlled at 70 ℃, and flow of electrolyte is 0ml/min, and electrolysis time is 2h.Electrolysis finishes to obtain product by acid precipitation, extraction, drying and other steps.After degraded, the weight-average molecular weight of xylogen has reduced by 55.4% compared with 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%.
Embodiment 3
Long be 10cm, wide is 10cm, thick is, in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, anode and cathode area is 10 * 10cm
2, interpole gap is 1cm, with titanium ruthenium net, makes anode, with foam copper, makes negative electrode, after injection purifying alkali lignin solution, carries out continuous electrolysis.The concentration of purifying alkali lignin solution is 5%, and stopper phenol amount of filling is 5% of xylogen quality, and the pH=11 of solution controls current density at 4mA/cm in electrolytic process
2, electrolysis temperature is controlled at 40 ℃, and flow of electrolyte is 20ml/min, and electrolysis finishes to obtain product by acid precipitation, extraction, drying and other steps.After degraded, the weight-average molecular weight of xylogen has reduced by 71.6% compared with 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%.
Embodiment 4
Long be 10cm, wide is 10cm, thick is, in the tilting cell body of 5cm, to place two pairs of cathode-anode plates, anode and cathode area is 10 * 10cm
2, interpole gap is 1.5cm, with titanium ruthenium iridium net, makes anode, with graphite felt, makes negative electrode, places rigid plastics net and play fixedly graphite felt electrode and prevent short circuit between the two poles of the earth, carries out continuous electrolysis after injecting straw lignin solution.The concentration of maize straw enzymolysis xylogen solution is 2%, and hydroquinone of polymerization retarder amount of filling is 1% of xylogen quality, and the pH=10 of solution controls current density at 2mA/cm in electrolytic process
2, at room temperature (25 ℃ of left and right) electrolysis, flow of electrolyte is 10ml/min.Electrolysis finishes to obtain product by acid precipitation, extraction, drying and other steps.After degraded, the weight-average molecular weight of xylogen has reduced by 76.4% compared with 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. the method for an electrochemical means lignin degrading, the cathode and anode that it is characterized in that used electrolyzer is skewed closely parallel placement, the oxygen that anode produces is reduced to hydrogen peroxide at cathode surface, and xylogen in electrolytic solution is produced to the effect of oxidation scission of link, and molecular weight is reduced; The active hydrogen that negative electrode produces simultaneously, to the oxidisability group reduction in xylogen fragment, increases hydroxy radical content; Wherein electrolyzer is long 10cm, wide 10cm, and thick is the tilting cell body of 5cm, in cell body, cathode and anode area is 10 * 10cm
2, and battery lead plate is the parallel placement of 10-80 degree with ground, interpole gap is 10～15mm, from Vertical Square, look up, anode under, negative electrode is upper, and anode and cathode can multilayer alternately place, and is not limited to two-layer.
2. the method for electrochemical means lignin degrading as claimed in claim 1, wherein electrochemical appliance Anodic material is optional one in ti-supported lead dioxide electric, titanium ruthenium, titanium ruthenium iridium, nickel, foam nickel electrode; Negative electrode material is optional one in graphite cake, the graphite felt through the fixing processing of anti-short circuit, copper, foam copper, stainless steel, foam nickel electrode.
3. the method for electrochemical means lignin degrading as claimed in claim 1, wherein xylogen concentration of aqueous solution is 1%-20% (mass ratio), and pH value is between 3-12, and stopper addition is the 0.5%-10% (mass ratio) of xylogen in solution; In electrolytic process, current density is 1-10mA/cm
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, wherein xylogen used is a kind of in 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 the nonhomogeneous system coexisting for degradation treatment lignin liquor or solid lignin and lignin liquor.
6. the method for electrochemical means lignin degrading as claimed in claim 3, wherein stopper is phenol, ethanol or Resorcinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110219209.3A CN102277591B (en) | 2011-08-02 | 2011-08-02 | Method for electrochemically degrading lignin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110219209.3A CN102277591B (en) | 2011-08-02 | 2011-08-02 | Method for electrochemically degrading lignin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102277591A CN102277591A (en) | 2011-12-14 |
| CN102277591B true CN102277591B (en) | 2014-03-05 |
Family
ID=45103315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110219209.3A Expired - Fee Related CN102277591B (en) | 2011-08-02 | 2011-08-02 | Method for electrochemically degrading lignin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102277591B (en) |
Families Citing this family (13)
| 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 |
| 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 |
| JP5887385B2 (en) * | 2014-07-25 | 2016-03-16 | シャープ株式会社 | Electrolyzer |
| 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 |
| CN106045141B (en) * | 2016-06-30 | 2023-04-18 | 浙江大学苏州工业技术研究院 | Method and device for electrochemically treating medical wastewater |
| CN106676574B (en) * | 2017-01-22 | 2018-08-28 | 河北工业大学 | A kind of method that electricity consumption catalysis technique hydrogenation depolymerization Spruce lignin prepares aromatic compound |
| CN106868862B (en) * | 2017-03-21 | 2019-02-22 | 张辰龙 | A kind of preparation method of the high antistatic hemp of degree of spinning |
| CN109680296B (en) * | 2018-12-24 | 2020-11-03 | 河北工业大学 | Method for preparing eugenol by reacting ortho-methoxyphenol group decomposed from lignin with additional allyl |
| 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 |
| US20230304170A1 (en) | 2020-06-18 | 2023-09-28 | 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 |
| 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003014A1 (en) * | 1985-11-13 | 1987-05-21 | The Minister Of Agriculture Fisheries And Food In | Electrochemical treatment of lignins |
| DE19723889A1 (en) * | 1997-06-06 | 1998-12-10 | Consortium Elektrochem Ind | System for the electrochemical delignification of lignocellulosic materials and method for its use |
| CA2267045A1 (en) * | 1998-03-26 | 1999-09-26 | Universite De Sherbrooke | Electrochemical hydrogenolysis of lignins on raney nickel based cathodes |
| CN1306026A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院广州化学研究所 | Process for preparing disperser by improving lignin |
| CN1361193A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院广州化学研究所 | Electrochemical process of preparing lignin in different molecular weight |
| CN1095514C (en) * | 2000-11-22 | 2002-12-04 | 中国科学院广州化学研究所 | Process for degradating chlorinated lignin and its derivatives |
| CN1528976A (en) * | 2003-09-30 | 2004-09-15 | 河北科技大学 | Cotton pulp black liquor treating method nad electrolysis apparatus thereof |
| EP1805336A1 (en) * | 2004-10-29 | 2007-07-11 | Phelps Dodge Corporation | Process for recovery of copper from copper-bearing material using pressure leaching, direct electrowinning and solvent/solution extraction |
| CA2722235A1 (en) * | 2008-05-14 | 2009-11-19 | Basf Se | Process for the electrochemical cleavage of lignin at a diamond electrode |
-
2011
- 2011-08-02 CN CN201110219209.3A patent/CN102277591B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003014A1 (en) * | 1985-11-13 | 1987-05-21 | The Minister Of Agriculture Fisheries And Food In | Electrochemical treatment of lignins |
| DE19723889A1 (en) * | 1997-06-06 | 1998-12-10 | Consortium Elektrochem Ind | System for the electrochemical delignification of lignocellulosic materials and method for its use |
| CA2267045A1 (en) * | 1998-03-26 | 1999-09-26 | Universite De Sherbrooke | Electrochemical hydrogenolysis of lignins on raney nickel based cathodes |
| CN1095514C (en) * | 2000-11-22 | 2002-12-04 | 中国科学院广州化学研究所 | Process for degradating chlorinated lignin and its derivatives |
| CN1306026A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院广州化学研究所 | Process for preparing disperser by improving lignin |
| CN1361193A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院广州化学研究所 | Electrochemical process of preparing lignin in different molecular weight |
| CN1528976A (en) * | 2003-09-30 | 2004-09-15 | 河北科技大学 | Cotton pulp black liquor treating method nad electrolysis apparatus thereof |
| EP1805336A1 (en) * | 2004-10-29 | 2007-07-11 | Phelps Dodge Corporation | Process for recovery of copper from copper-bearing material using pressure leaching, direct electrowinning and solvent/solution extraction |
| CA2722235A1 (en) * | 2008-05-14 | 2009-11-19 | Basf Se | Process for the electrochemical cleavage of lignin at a diamond electrode |
| CN102027161A (en) * | 2008-05-14 | 2011-04-20 | 巴斯夫欧洲公司 | Method for electrochemically cleaving lignin on a diamond electrode |
Non-Patent Citations (4)
| Title |
|---|
| Extraction and characterization of original lignin and hemicelluloses from wheat straw;Xiao-Feng Sun etc.;《Agricultural and food chemistry》;20050201;第53卷(第4期);第860-870页 * |
| Xiao-Feng Sun etc..Extraction and characterization of original lignin and hemicelluloses from wheat straw.《Agricultural and food chemistry》.2005,第53卷(第4期), |
| 木质素的电化学氧化;薛建军 等;《林产化学与工业》;20010630;第21卷(第2期);第5-8页 * |
| 薛建军 等.木质素的电化学氧化.《林产化学与工业》.2001,第21卷(第2期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102277591A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102277591B (en) | Method for electrochemically degrading lignin | |
| Yang et al. | Performance and long-term stability of CO2 conversion to formic acid using a three-compartment electrolyzer design | |
| CN101748423B (en) | Efficient electrochemical reactor of electro-catalysis in-situ hydrogen peroxide | |
| US10351879B2 (en) | Method and system for electro-assisted hydrogen production from organic material | |
| CN204162485U (en) | A kind of organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption | |
| CN104176797A (en) | Low-energy-consumption electrochemical treatment device and method for degradation-resistant organic wastewater | |
| CN102864463A (en) | H2 collection system for kitchen wastes | |
| CN108147505B (en) | Device and method for producing hydrogen by coupling solar-driven wastewater treatment | |
| CN106676574A (en) | Method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through electro-catalysis technology | |
| CN204111387U (en) | A kind of employing anion-exchange membrane solid state electrolyte electrolytic cell assembly | |
| CN106480102A (en) | A kind of method for improving methane production using electrolysis auxiliary anaerobe | |
| CN113373464B (en) | Method for preparing cyclane by electrocatalytic conversion of lignin derivative | |
| Meng et al. | Study of depolymerization of cotton cellulose by Pb/PbO2 anode electrochemical catalysis in sulfuric acid solution | |
| CN204151114U (en) | A kind of cloth water structure of SPE electrolyzer | |
| CN106987862A (en) | A kind of method of the electrochemical degradation lignin in eutectic solvent | |
| CN104192957B (en) | A kind of employing anion-exchange membrane solid state electrolyte electrolytic cell assembly | |
| CN113249740A (en) | Method for preparing graphene by electrochemical continuous and synchronous stripping and reduction | |
| CN102701336A (en) | Power-saving method for electrolysis treatment of wastewater | |
| CN204198463U (en) | A kind of continuum micromeehanics formula solid state electrolyte electric tank cathode system | |
| CN112899042A (en) | Electrochemical mild and efficient hydrogenation method for pyrolysis oil | |
| CN105063108B (en) | A kind of intensifying method of biology electrodialysis production malic acid | |
| CN102534650B (en) | Method for preparing glucose by electrochemically degrading fiber oligosaccharide | |
| CN102011135A (en) | Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte | |
| Wang et al. | Promoting transfer of endogenous electrons well increases the carbon and energy efficiency of lignocellulosic biomass conversion to fuels and chemicals | |
| CN103880246B (en) | A kind of ECH-SBR combination process innoxious degraded Pentachlorophenol method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140305 Termination date: 20190802 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |