CN103131021A - Method for improving lignin activity by wet ball milling - Google Patents
Method for improving lignin activity by wet ball milling Download PDFInfo
- Publication number
- CN103131021A CN103131021A CN2013100557608A CN201310055760A CN103131021A CN 103131021 A CN103131021 A CN 103131021A CN 2013100557608 A CN2013100557608 A CN 2013100557608A CN 201310055760 A CN201310055760 A CN 201310055760A CN 103131021 A CN103131021 A CN 103131021A
- Authority
- CN
- China
- Prior art keywords
- ball
- ball milling
- acid
- xylogen
- activity
- 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.)
- Pending
Links
Landscapes
- Crushing And Grinding (AREA)
Abstract
The invention discloses a method for improving lignin activity by wet ball milling. Under normal-temperature and normal-pressure, a material and processing liquid with a ratio of 1:1-1:5 are placed in a ball milling tank; 10-100 milling balls are added; ball milling is carried out for 30-180min in a sealed condition with a rotation speed of 300-1000rpm. A sample obtained after ball milling is washed and filtered, and is subjected to vacuum drying under a temperature of 35-80 DEG C. Aiming at different purposes of lignin, different processing liquids, solid-liquid ratios, milling ball numbers, rotation speeds, and processing times are selected. The method provided by the invention has the advantages of mild processing conditions, low cost, and easy operation. With the method, lignin active group content can be substantially improved, lignin polydispersity is reduced, and lignin further high-value conversion and utilization are facilitated.
Description
Technical field
The invention belongs to xylogen preconditioning technique field, can significantly improve by the method xylogen active group content and reduce its polymolecularity, prepare high value added product thereby be conducive to the xylogen catalyzed conversion.
Background technology
Xylogen (Lignin) is the complicated macromolecular compound that is present in the wooden part of most of land plant, enormous amount, content in lignocellulose is 15%-30%, be to be only second to cellulosic natural organic matter resource, and approximately regenerates with the speed of 50,000,000,000 tons every year.Having the groups such as aromatic nucleus, alcoholic extract hydroxyl group, phenolic hydroxyl group, carboxyl, methoxyl group, conjugated double bond in lignin molecule, can carry out the number of chemical reaction, is the potential industrial chemicals of a kind of tool, can be for the preparation of material, chemical, fuel wet goods.At present, the xylogen on market is mainly as the byproduct of pulp and paper industry, approximately 5,000 ten thousand tons of annual production.Yet the mankind also are in the starting stage to the utilization of xylogen, the act as a fuel burning or use as cheap products such as the additives of material of construction of most of xylogen.
At present, separate the xylogen that obtains and have the lower problem of reactive behavior.Reason is: be in delignification's technique on the one hand, the part active group of natural lignin is destroyed; On the other hand, in xylogen, most of active group participates in the Cheng Jian of molecular structure, and the latter is a major reason that affects lignin reaction's activity.
Improve at present the research of lignin reaction's activity mainly by chemical modification, comprising: amination, sulfonation, sulfuration, phenolate, oxidation, graft copolymerization, condensation and modification etc.Chemical modification can increase the reactive behavior of xylogen to a certain extent, but exist still that energy consumption is high, the problem such as the homogeneity of easy generation pollution and molecule is bad.Therefore the activation method of studying a kind of more cheap efficient xylogen has certain necessity.
Summary of the invention
[goal of the invention] the present invention processes ball milling coupling processing liquid to xylogen, realize under normal temperature and pressure, the low-cost purpose that improves the xylogen activity.
[design of the present invention] ball milling is as a kind of efficient pulverizing means, become the focus of research, its advantage is to make the particle of material to reach superfine on the one hand, can effectively increase the specific surface of material particles, on the other hand, be that there is Mechanochemical Effect in it, can bring out some and utilize thermodynamics to be difficult to the chemical reaction (Peters K.Frankfurt:1962,78 ~ 79) that maybe can't carry out.Previous experiments studies show that dry xylogen easy caking and cause mill efficiency low and cause the homogeneity of material poor in mechanical milling process.Yuan Li etc. (2012) have studied the diluted acid under the ultrasonic pretreatment-milling system degraded birch wood chip, find that the milling of dilute acid system can be hydrolyzed the lignocellulose of wood chip at normal temperatures and pressures preferably, and xylogen is partly had certain destruction.And the variation of carbohydrate in the wood chip has mainly been paid close attention in this research, does not study the variation of xylogen active group.Based on above reason, the present invention proposes the method that wet ball grinding improves the xylogen activity.
[technical solution of the present invention]
1, a kind of wet ball grinding improves the method for xylogen activity, it is characterized in that the method includes the steps of:
Step 1, screening: the xylogen sample is carried out sieving for standby;
Step 2, charging: add by a certain percentage the material of step 1 gained and treatment solution in ball grinder and add the ball milling pearl of some amount;
Step 3, ball milling: to the material ball milling certain hour that fills;
Step 4, washing and filtration: wash the material after ball milling and filtration in step 3 with water;
Step 5, drying: step 4 gained solid substance is carried out vacuum-drying;
In step 1, screen cloth is 20 orders～40 orders.
In step 2, the charge amount of material is 1/3 ~ 2/3 of tank volume; Treatment solution concentration is 1% ~ 15%, treatment solution comprises acid (formic acid, acetic acid, propionic acid, succinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, citric acid etc.), alkali (sodium hydroxide, potassium hydroxide, calcium hydroxide,, ammoniacal liquor etc.), salt (sodium acetate, potassium acetate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, sodium carbonate, sodium bicarbonate etc.) and organism (benzene,toluene,xylene, tetraline, phenol, anthraquinone etc.) and the buffered soln that is comprised of arbitrary two classes in the acid-alkali salt three; Solid-to-liquid ratio is 1:1 ~ 1:5; The reprinting amount of ball milling pearl is 10 ~ 100;
Ball mill described in step 3 is planetary ball mill, tank abrading-ball grinding machine or particle sphere grinding machine etc.; Grinding pot is looked the stainless cylinder of steel of material different choice, agate tank or zirconium white tank etc.; The ball milling pearl looks material different choice Stainless Steel Ball, agate ball, zirconia ball; Grind 300～1000 rev/mins of revolutions; Milling time 10～180min.
With the material after the water cleaning ball milling of 5 ~ 10 times of volumes, adopt the mode of suction filtration to filter in step 4;
In step 5, vacuum drying temperature is 35 ~ 80 ℃, and be 12 ~ 36h time of drying.
The present invention has following characteristics and advantage:
1. the present invention replaces traditional chemical modification method to improve lignin reaction's activity with wet ball grinding, and process in airtight at normal temperatures and pressures ball grinder and carry out, easy handling, and processing cost is cheap, has good environment friendly.
2. a kind of wet ball grinding of the present invention improves the method for xylogen activity, can effectively improve the content of xylogen active group and reduce its polymolecularity, has with respect to chemical modification that cost is low, eco-friendly advantage.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
The xylogen powder is crossed 40 mesh sieves, select TJ-1 type particle sphere grinding machine, then itself and 4% hydrochloric acid soln are 1:4(w/v in proportion) join in zirconium white material ball grinder, the quantity of ball milling pearl is by 1:2(quality of material g/ ball milling pearl number) add, with 500rpm rotation ball milling 30min, xylogen sample after ball milling divides and washs suction filtration 4 times with the water of 5 times of volumes.Resulting solid substance is at 40 ℃ of vacuum-drying 24h.Dried sample is measured respectively content and molecular weight and the polymolecularity of active group.By phenolic hydroxyl group and carboxyl-content in nonaqueous phase potentiometric determination sample; Molecular weight and polymolecularity thereof by gel permeation chromatography (GPC/SEC) working sample.Sample phenol hydroxyl value content and carboxyl-content after wet ground is respectively after testing: 7.14mmol/g, 7.35mmol/g; Higher than raw sample: 5.0mmol/g, 6.73mmol/g.Sample polymolecularity after wet ball grinding is simultaneously: PD=1.88, and lower than former state (PD=2.53).
Embodiment 2
The xylogen powder is crossed 20 mesh sieves, select TJ-1 type particle sphere grinding machine, then itself and 10% toluene are 1:2(w/v in proportion) join in zirconium white material ball grinder, the quantity of ball milling pearl is by 1:3(quality of material g/ ball milling pearl number) add, with 1000rpm rotation ball milling 30min, xylogen sample after ball milling divides and washs suction filtration 5 times with the water of 10 times of volumes.Resulting solid substance is at 40 ℃ of vacuum-drying 36h.Dried sample is measured respectively content and molecular weight and the polymolecularity of active group.By phenolic hydroxyl group and carboxyl-content in nonaqueous phase potentiometric determination sample; Molecular weight and polymolecularity thereof by gel permeation chromatography (GPC/SEC) working sample.Sample phenol hydroxyl value content and carboxyl-content after wet ground is respectively after testing: 5.87mmol/g, 6.20mmol/g; Higher than raw sample: 5.0mmol/g, 6.73mmol/g.Sample polymolecularity after wet ball grinding is simultaneously: PD=2.40, and lower than former state (PD=2.53).
Claims (6)
1. a wet ball grinding improves the method for xylogen activity, it is characterized in that the method includes the steps of:
Step 1, screening: the xylogen sample is carried out sieving for standby;
Step 2, charging: add by a certain percentage the material of step 1 gained and treatment solution in ball grinder and add the ball milling pearl of some amount;
Step 3, ball milling: to the material ball milling certain hour that fills;
Step 4, washing and filtration: wash the material after ball milling and filtration in step 3 with water;
Step 5, drying: step 4 gained solid substance is carried out vacuum-drying.
2. a kind of wet ball grinding improves the method for xylogen activity as claimed in claim 1, and it is characterized in that: in step 1, screen cloth is 20 orders～40 orders.
3. a kind of wet ball grinding improves the method for xylogen activity as claimed in claim 1, and it is characterized in that: in step 2, the charge amount of material is 1/3 ~ 2/3 of tank volume; Treatment solution concentration is 1% ~ 15%, treatment solution comprises acid (formic acid, acetic acid, propionic acid, succinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, citric acid etc.), alkali (sodium hydroxide, potassium hydroxide, calcium hydroxide,, ammoniacal liquor etc.), salt (sodium acetate, potassium acetate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, sodium carbonate, sodium bicarbonate etc.) and organism (benzene,toluene,xylene, tetraline, phenol, anthraquinone etc.) and the buffered soln that is comprised of arbitrary two classes in the acid-alkali salt three; Solid-to-liquid ratio is 1:1 ~ 1:5; The reprinting amount of ball milling pearl is 10 ~ 100.
4. a kind of wet ball grinding improves the method for xylogen activity as claimed in claim 1, and it is characterized in that: ball mill described in step 3 is planetary ball mill, tank abrading-ball grinding machine or particle sphere grinding machine etc.; Grinding pot is looked the stainless cylinder of steel of material different choice, agate tank or zirconium white tank etc.; The ball milling pearl looks material different choice Stainless Steel Ball, agate ball, zirconia ball; Grind 300～1000 rev/mins of revolutions; Milling time 10～180min.
5. a kind of wet ball grinding improves the method for xylogen activity as claimed in claim 1, it is characterized in that: clean material after ball milling with the water of 5 ~ 10 times of volumes in step 4, adopt the mode of suction filtration to filter.
6. as claimed in claim 1, it is characterized in that: in step 5, vacuum drying temperature is 35 ~ 80 ℃, and be 12 ~ 36h time of drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100557608A CN103131021A (en) | 2013-02-21 | 2013-02-21 | Method for improving lignin activity by wet ball milling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100557608A CN103131021A (en) | 2013-02-21 | 2013-02-21 | Method for improving lignin activity by wet ball milling |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103131021A true CN103131021A (en) | 2013-06-05 |
Family
ID=48491512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100557608A Pending CN103131021A (en) | 2013-02-21 | 2013-02-21 | Method for improving lignin activity by wet ball milling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103131021A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483597A (en) * | 2013-08-26 | 2014-01-01 | 中国林业科学研究院林产化学工业研究所 | Method for modifying enzymatic hydrolysis lignin by alkali activation |
| CN108456313A (en) * | 2018-03-05 | 2018-08-28 | 安徽工业大学 | A kind of method of liquid nitrogen coupling ball milling pretreatment extraction lignin from biomass |
| CN109161031A (en) * | 2018-07-02 | 2019-01-08 | 北京林业大学 | A method of lignin is efficiently separated based on diluted acid pre-preg |
| CN109675686A (en) * | 2018-11-29 | 2019-04-26 | 刘永 | A kind of material filling method improving ball mill grinding efficiency |
| CN113461978A (en) * | 2021-07-06 | 2021-10-01 | 天津科技大学 | Preparation method for preparing high-yield lignin nanoparticles with assistance of ball milling pretreatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2094053C1 (en) * | 1995-06-20 | 1997-10-27 | Институт солнечно-земной физики СО РАН | Method of bacterioadsorbing agent producing |
| CN101230546A (en) * | 2008-02-28 | 2008-07-30 | 中国石油化工股份有限公司 | Combined pretreatment method of wood cellulose and system thereof |
| CN101928466A (en) * | 2010-03-30 | 2010-12-29 | 湖南师范大学 | Rubber reinforcing agent and preparation method and application thereof |
-
2013
- 2013-02-21 CN CN2013100557608A patent/CN103131021A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2094053C1 (en) * | 1995-06-20 | 1997-10-27 | Институт солнечно-земной физики СО РАН | Method of bacterioadsorbing agent producing |
| CN101230546A (en) * | 2008-02-28 | 2008-07-30 | 中国石油化工股份有限公司 | Combined pretreatment method of wood cellulose and system thereof |
| CN101928466A (en) * | 2010-03-30 | 2010-12-29 | 湖南师范大学 | Rubber reinforcing agent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄锦浩: "木质素/聚烯烃复合材料的制备及性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, 15 December 2012 (2012-12-15), pages 16 - 17 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483597A (en) * | 2013-08-26 | 2014-01-01 | 中国林业科学研究院林产化学工业研究所 | Method for modifying enzymatic hydrolysis lignin by alkali activation |
| CN103483597B (en) * | 2013-08-26 | 2016-01-13 | 中国林业科学研究院林产化学工业研究所 | A kind of method of alkali activation modification enzymolysis xylogen |
| CN108456313A (en) * | 2018-03-05 | 2018-08-28 | 安徽工业大学 | A kind of method of liquid nitrogen coupling ball milling pretreatment extraction lignin from biomass |
| CN109161031A (en) * | 2018-07-02 | 2019-01-08 | 北京林业大学 | A method of lignin is efficiently separated based on diluted acid pre-preg |
| CN109161031B (en) * | 2018-07-02 | 2020-02-21 | 北京林业大学 | Method for efficiently separating lignin based on dilute acid preimpregnation |
| CN109675686A (en) * | 2018-11-29 | 2019-04-26 | 刘永 | A kind of material filling method improving ball mill grinding efficiency |
| CN109675686B (en) * | 2018-11-29 | 2021-01-26 | 刘永 | Material filling method for improving grinding efficiency of ball mill |
| CN113461978A (en) * | 2021-07-06 | 2021-10-01 | 天津科技大学 | Preparation method for preparing high-yield lignin nanoparticles with assistance of ball milling pretreatment |
| CN113461978B (en) * | 2021-07-06 | 2023-01-10 | 天津科技大学 | Preparation method for preparing high-yield lignin nanoparticles with assistance of ball milling pretreatment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103131021A (en) | Method for improving lignin activity by wet ball milling | |
| CN102101915B (en) | Separation method for agriculture and forestry biomass components | |
| CN102212976B (en) | Method for separating bagasse cellulose from lignin | |
| CN103998617B (en) | The manufacture method of lignin analyte | |
| CN105860090B (en) | The method of high activity lignin and its obtained lignin are extracted from biomass | |
| CN112851977B (en) | Lignin nano-particles and preparation method and application thereof | |
| CN103088692B (en) | Selective Separation lignin and cellulosic method from lignocellulose-like biomass | |
| CN107200851A (en) | A kind of method that eutectic solvent prepares nano lignin | |
| CN102813147B (en) | Preparation method of jujube residue insoluble dietary fiber powder | |
| CN102733224A (en) | Method for separating corncob cellulose by using ionic liquid | |
| CN103305492B (en) | Method for extracting high-purity pharmaceutical grade bromelain | |
| CN113307983A (en) | Method for separating lignin by green solvent quickly and in high yield | |
| CN102391390A (en) | Tobacco extraction method based on steam explosion | |
| CN103131802B (en) | Process for producing xylose by lignocellulose biomass | |
| CN103964432A (en) | Method for preparing granular activated carbon from lignin | |
| CN104558210A (en) | Method for preparing nano-cellulose | |
| CN103450256B (en) | Comprehensive utilization method of defatted rice bran | |
| CN105297511A (en) | Separation method of organic constituent in agricultural waste | |
| CN103965365B (en) | A kind of preparation method of apple residue Microcrystalline Cellulose | |
| CN103849665A (en) | Method for pretreating lignocellulose by using carboxyl functionalized ionic liquid solution | |
| WO2022052775A1 (en) | Production process of non-adhesive formaldehyde-free fiber board for straw co-production of fulvic acid | |
| CN108383926B (en) | Method for co-producing gel type and emulsion type pectin by using chicory/taro meal | |
| CN103949223B (en) | A kind of preparation method of the adsorbent for removing fermentation inhibitor | |
| CN104743553A (en) | Method and device for co-production of furfural and active carbon | |
| CN106832330A (en) | The technique of recovery and the purification of residual lignin after a kind of steam blasting pretreatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130605 |