CN102251428A - Method for handling black liquor produced by handling straw-like lignocellulosic materials - Google Patents
Method for handling black liquor produced by handling straw-like lignocellulosic materials Download PDFInfo
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Abstract
The invention provides a method for handling black liquor produced by handling straw-like lignocellulosic materials. The method comprises the following steps: after carrying out alkali treatment on the straw-like lignocellulosic materials, carrying out solid-liquid separation on the obtained product so as to obtain straw residues and black liquor; carrying out lignin flocculation on the black liquor; carrying out solid-liquid separation on the black liquor subjected to flocculation so as to obtaine a flocculate rich in lignin and black liquor; and re-handling and then recycling the obtained black liquor. In the method, through handing, re-handling and then recycling the black liquor produced by handling straw-like lignocellulosic materials, the cost of enterprise sewage treatment is lowered while the lignin with high heat value is obtained, therefore, the method disclosed by the invention has the advantages of high higher economic and social benefits.
Description
Technical field
The present invention relates to technical field of biomass chemical engineering, be specially the processing method that the straw lignocellulose raw material is handled the black liquor that produces.
Background technology
The main component of straw lignocellulose resource is cellulose, hemicellulose and lignin.Wherein, cellulose, hemicellulose are the sources of fermentable sugars.Lignin is that (the three-dimensional netted polymer substance that O-) is formed by connecting is complicated aromatic polymer by carbon-carbon bond (C-C) and ehter bond by phenylpropyl alcohol alkyl structure unit; Because its aromatic series character, side chain aliphatic characteristic and various functional group, lignin can become energy substance and the important chemical material as oil.
Ethanol is commonly called as alcohol, is not only a kind of very important Organic Chemicals and solvent, and is considered to the most promising liquid fuel of alternative petroleum-type non-renewable resources because of its renewable and environmentally safe.
The market scale of China's alcohol fuel just sharply enlarges.Is this class raw material recovery energy problem the most widely with the straw lignocellulose for feedstock production ethanol.Usually, with the straw lignocellulose is feedstock production ethanol, at first need plant fiber material acid or alkali treatment, carry out Separation of Solid and Liquid after boiling, the washing, separating obtained black liquor is called as black liquor, wherein contains lignin, hemicellulose and the cellulosic catabolite and the organic acid etc. of stripping from the processing raw material.
Consider from economic benefit, in the process that with the straw lignocellulose is feedstock production ethanol, produced a large amount of black liquor at present, in the process of sewage disposal, certainly will strengthen the fund input of enterprise's sewage disposal; A large amount of lignins has very high economic worth in the black liquor simultaneously, lignin is a kind of aromatic polymer compound, and the lignosulphonates that the use sulphite process is handled behind the black liquor can be used as adhesive, chelating agent, industrial remover, water correction agent, emulsifying agent and emulsion stabilizer, tannin replenishers, cement additire, oil drilling dispersant and soil stabilizer etc.In addition, also available lignosulphonic acid prepares vanilla element, vanillic acid etc.Sulfate process is handled the aliphatic compound that the back black liquor can prepare sulfur-bearing, as dimethyl sulfoxide (DMSO), dimethyl sulfone and dimethylsulphide etc.
When the objective of the invention is to reduce enterprise's cost of sewage disposal, improve economic benefit of enterprises.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of straw lignocellulose raw material to handle the processing method of the black liquor that produces.
Straw lignocellulose raw material provided by the invention is handled the processing method of the black liquor that produces, it comprises and obtains stalk slag and black liquor I to carrying out Separation of Solid and Liquid after the plain raw material alkali treatment of stalk fibrid, black liquor I is carried out the lignin flocculation, and the black liquor I Separation of Solid and Liquid after will flocculating then obtains being rich in the flocculate and the black liquor II of lignin.
Further, described processing method also comprise black liquor II detected alkali concn after, add aqueous slkali or concentrate.
Wherein, above-mentionedly can adopt any method well known in the art to concentrate, preferably to adopt the economic benefits and social benefits inspissator to concentrate concentrating of black liquor.
Further, described black liquor II reaches 1.0～2.0% by adding aqueous slkali or concentrating back NaOH content.Unless stated otherwise, the used percentage of the present invention is mass percent, and ratio is a mass ratio.
Further, in described processing method, be 1.0～2.0% alkali lye or to regulate NaOH content be 1.0～2.0% black liquor II with NaOH content, under 90～120 ℃,, the plain raw material of stalk fibrid is carried out alkali treatment to the plain material cooking of stalk fibrid 0.5～2 hour.
Further, describedly comprise that to carrying out Separation of Solid and Liquid after the plain raw material alkali treatment of stalk fibrid earlier the plain raw material of the stalk fibrid after the alkali treatment being carried out first Separation of Solid and Liquid is separated black liquor and solid straws slag first, then obtain secondary separation black liquor and solid straws slag, separate black liquor first and the secondary separation black liquor is merged into black liquor I described with carrying out once more Separation of Solid and Liquid behind this solid straws slag of hot wash.
Further, the employed equipment of described Separation of Solid and Liquid can be the acroll press washer group, and described acroll press washer group can be by being composed in series by the strand cage by 4～6 acroll press washers.
Further, in described processing method, flocculate with alkaline flocculant.
Further, described alkaline flocculant contains: Ca (OH)
220～30%, active white clay 5～10%, diatomite 5～10%, plant ash 5～10% and NaOH content are 30%～32% industrial aqueous slkali 40～60%.
Further, the addition of described alkaline flocculant is 1 of black liquor volume～2 ‰.
The present invention can adopt any method well known in the art that flocculate is separated, and preferably adopts the plate compression unit, and wherein, described plate compression unit can be composed in parallel by 3～4 platen frame filter presses.
Straw lignocellulose raw material of the present invention is any straw lignocellulose raw material well known in the art, as maize straw, rape stalk, jowar stalk, wheat stalk, rice straw etc.
Advantage of the present invention:
The invention provides a kind of processing method of straw lignocellulose ethanol black liquor, compare with the processing method of traditional paper industry black liquor, the lignin goods content height that the inventive method obtains from black liquor, impurity is few; Handle the reuse after concentrating of back black liquor, its effect aspect the alkali treatment straw lignocellulose is handled back stalk slag after testing with directly identical with the alkali treatment straw lignocellulose usually, and is identical with the stalk slag component of common production; The present invention is in the black liquor recovery production process, energy consumption is higher in direct alkali lye production, substitute part coal, advantage that surcharge is high but the lignin that extracts has the calorific value height, can be used for enterprise, reduced the cost of enterprise's sewage disposal, this method has higher economic and social benefit.
The specific embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Get the maize straw 10kg of pulverizing, add concentration and be 1.5% alkali lye 45L 100 ℃ of following boilings 1 hour, through the acroll press washer group first Separation of Solid and Liquid get and separate black liquor and solid straws slag first, this solid straws slag adopts the 20kg hot wash, through acroll press washer group Separation of Solid and Liquid once more, isolated washing black liquid is that the secondary separation black liquor is merged into black liquor I with the aforesaid black liquor that separates first, and isolated stalk slag is standby.
Add the flocculant of 1.5 ‰ (v/v) in the above-mentioned black liquor I, stir the back flocculation, obtained being rich in the flocculate solid and the black liquor II of lignin after the plate and frame filter press Separation of Solid and Liquid in 0.5 hour; Wherein, the proportioning of described flocculant is: 25% Ca (OH)
2, 7% active white clay, 8% diatomite, 10% plant ash and 50% industrial aqueous slkali (NaOH content 31.6%).
Embodiment 2
To implement, add alkali through plate and frame filter press Separation of Solid and Liquid gained black liquor II according to embodiment 1, the alkali concn that makes this black liquor be 2.0%.
Get the maize straw 10kg of pulverizing, add above-mentioned concentration and be 2.0% black liquor 45L 120 ℃ of following boilings 1.0 hours, through the acroll press washer group first Separation of Solid and Liquid get and separate black liquor and solid straws slag first, this solid straws slag adopts the 20kg hot wash, through acroll press washer group Separation of Solid and Liquid once more, isolated washing black liquid is that the secondary separation black liquor is merged into black liquor I with the aforesaid black liquor that separates first, and isolated stalk slag is standby.
Add the flocculant of 1.0 ‰ (v/v) in the above-mentioned black liquor I, stir the back flocculation, obtained being rich in the flocculate solid and the black liquor II of lignin after the plate and frame filter press Separation of Solid and Liquid in 0.5 hour; Wherein, the proportioning of described flocculant is: 30% Ca (OH)
2, 10% active white clay, 5% diatomite, 5% plant ash and 5% industrial aqueous slkali (NaOH content 31.6%).
Embodiment 3
To implement, concentrate with the economic benefits and social benefits inspissator through plate and frame filter press Separation of Solid and Liquid gained black liquor II according to embodiment 1, making this alkali concn that concentrates the back black liquor be 1.0%.
Get the maize straw 5kg of pulverizing, add above-mentioned concentration and be 1.0% concentrated back black liquor 22.5L 90 ℃ of following boilings 2.0 hours, get through acroll press washer group Separation of Solid and Liquid and to separate black liquor and solid straws slag first, this solid straws slag adopts the 10kg hot wash, through acroll press washer group Separation of Solid and Liquid once more, isolated washing black liquid is that the secondary separation black liquor is merged into black liquor I with the aforesaid black liquor that separates first, and isolated stalk slag is standby.
Add the flocculant of 2.0 ‰ (v/v) in the above-mentioned black liquor I, stir the back flocculation, obtained being rich in the flocculate solid and the black liquor II of lignin after the plate and frame filter press Separation of Solid and Liquid in 0.5 hour.Wherein, the proportioning of described flocculant is: 20% Ca (OH)
2, 5% active white clay, 10% diatomite, 10% plant ash and 55% industrial aqueous slkali (NaOH content 31.6%).
Embodiment 4
Implement according to embodiment 1, add alkali through plate and frame filter press Separation of Solid and Liquid gained black liquor II, the alkali concn that makes this black liquor is 1.5%, be back to then the plain raw material alkali treatment of stalk fibrid, after recycling 5 times, the secondary flocculation, II concentrates with the economic benefits and social benefits inspissator through plate and frame filter press Separation of Solid and Liquid gained black liquor, making this alkali concn that concentrates the back black liquor is 2.0%, as the standby concentrated back black liquor of present embodiment.
Get the maize straw 4kg of pulverizing, add above-mentioned concentration and be 2.0% standby concentrated back black liquor 18L 110 ℃ of following boilings 1.5 hours, separate to such an extent that separate black liquor and solid straws slag first first through acroll press washer group solid-liquid, this solid straws slag adopts the 8kg hot wash, through acroll press washer group Separation of Solid and Liquid once more, isolated washing black liquid is that the secondary separation black liquor is merged into black liquor I with the aforesaid black liquor that separates first, and isolated stalk slag is standby.
Add the flocculant of 1.0 ‰ (v/v) in the above-mentioned black liquor I, stir the back flocculation, obtained being rich in the flocculate solid and the black liquor II of lignin after the plate and frame filter press Separation of Solid and Liquid in 0.5 hour.Wherein, the proportioning of described flocculant is: 30% Ca (OH)
2, 10% active white clay, 10% diatomite, 10% plant ash and 40% industrial aqueous slkali (NaOH content 31.6%).
Experimental example 1
With isolated standby stalk slag sample presentation detection after alkali treatment among the embodiment 1～4, result's (table 1) shows, use contains the identical alkali lye of alkali concn, adds the alkali black liquor, concentrates the concentrate of black liquor, secondary flocculation black liquor afterwards, straw lignocellulose is carried out alkali treatment, the standby stalk slag ingredient basically identical of gained, as seen its treatment effect is consistent.
The result that standby stalk slag sample presentation detects among table 1: the embodiment 1～4
| Moisture/% | Cellulose/% | Hemicellulose/% | Lignin/% | Ash content/% | |
| Embodiment 1 | 72.58 | 60.63 | 25.55 | 8.85 | 6.92 |
| Embodiment 2 | 75.80 | 61.93 | 25.72 | 7.06 | 6.54 |
| Embodiment 3 | 74.36 | 61.36 | 25.13 | 6.94 | 7.66 |
| Embodiment 4 | 74.18 | 60.91 | 25.80 | 8.34 | 6.93 |
Annotate: cellulose, half fiber, lignin, content of ashes are content in the butt in the table
Experimental example 2
With among the embodiment 1～4 through the plate and frame filter press Separation of Solid and Liquid, the flocculate solid sample presentation that is rich in lignin that obtains detects, result's (table 2) shows, use contains the identical alkali lye of alkali concn, adds the alkali black liquor, concentrates the concentrate of black liquor, secondary flocculation black liquor afterwards, straw lignocellulose is carried out alkali treatment, the gained black liquor through flocculation after the plate and frame filter press Separation of Solid and Liquid, the flocculate solid constituent basically identical that is rich in lignin that obtains, all contain higher lignin, as seen its treatment effect is consistent.
Be rich in the result of the flocculate solid sample presentation detection of lignin among table 2: the embodiment 1～4
| Moisture/% | Lignin/% | |
| Embodiment 1 | 75.32 | 75.85 |
| Embodiment 2 | 75.50 | 74.46 |
| Embodiment 3 | 78.37 | 76.38 |
| Embodiment 4 | 75.97 | 84.40 |
Annotate: lignin content is a content in the butt in the table
Though the present invention is described in detail above to have used general explanation and specific embodiment, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a straw lignocellulose raw material is handled the processing method of the black liquor that produces, it comprises and obtains stalk slag and black liquor I to carrying out Separation of Solid and Liquid after the plain raw material alkali treatment of stalk fibrid, black liquor I is carried out the lignin flocculation, and the black liquor I Separation of Solid and Liquid after will flocculating then obtains being rich in the flocculate and the black liquor II of lignin.
2. processing method according to claim 1 is characterized in that, also comprise black liquor II detected alkali concn after, add aqueous slkali or concentrate.
3. processing method according to claim 2 is characterized in that, described black liquor II reaches 1.0～2.0% by adding aqueous slkali or concentrating back NaOH content.
4. according to each described processing method of claim 1～3, it is characterized in that, with NaOH content is 1.0～2.0% alkali lye or to regulate NaOH content be 1.0～2.0% black liquor II, under 90～120 ℃,, the plain raw material of stalk fibrid is carried out alkali treatment to the plain material cooking of stalk fibrid 0.5～2 hour.
5. processing method according to claim 1, it is characterized in that, describedly comprise that to carrying out Separation of Solid and Liquid after the plain raw material alkali treatment of stalk fibrid earlier the plain raw material of the stalk fibrid after the alkali treatment being carried out first Separation of Solid and Liquid is separated black liquor and solid straws slag first, then obtain secondary separation black liquor and solid straws slag, separate black liquor first and the secondary separation black liquor is merged into black liquor I described with carrying out once more Separation of Solid and Liquid behind this solid straws slag of hot wash.
6. processing method according to claim 5 is characterized in that, the employed equipment of described Separation of Solid and Liquid is the acroll press washer group.
7. processing method according to claim 1 is characterized in that, flocculates with alkaline flocculant.
8. processing method according to claim 7 is characterized in that, described alkaline flocculant contains: Ca (OH)
220～30%, active white clay 5～10%, diatomite 5～10%, plant ash 5～10% and NaOH content are 30%～32% industrial aqueous slkali 40～60%.
9. processing method according to claim 7 is characterized in that, the addition of described alkaline flocculant is 1 of black liquor volume～2 ‰.
10. according to each described processing method of claim 7～9, it is characterized in that the employed equipment of black liquor Separation of Solid and Liquid after the described flocculation is the plate compression unit.
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| CN 201110212170 CN102251428A (en) | 2011-07-27 | 2011-07-27 | Method for handling black liquor produced by handling straw-like lignocellulosic materials |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104032612A (en) * | 2014-06-17 | 2014-09-10 | 毛林涛 | Method for extracting lignin from alkaline straw pulp black liquor |
| CN105296568A (en) * | 2015-11-05 | 2016-02-03 | 中国科学院广州能源研究所 | Method for recycling alkali treatment lignocellulose waste fluid |
| CN105838756A (en) * | 2016-05-12 | 2016-08-10 | 中国科学院广州能源研究所 | Water-saving and emission-reduction technology for producing sugar through enzymolysis of lignocellulose treated with alkali |
| CN108048297A (en) * | 2017-11-20 | 2018-05-18 | 中国科学院广州能源研究所 | A kind of device applied to oxygenation pretreatment lignocellulosic enzymolysis saccharification water-saving and emission-reducing technique |
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| CN1316567A (en) * | 2000-04-05 | 2001-10-10 | 李风宁 | Process for treating black digestion liquid generated by paper alkali pulping |
| CN1697901A (en) * | 2003-06-18 | 2005-11-16 | 玉米浆及纸制品公司 | Method for producing corn stalk pulp and paper products from corn stalk pulp |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316567A (en) * | 2000-04-05 | 2001-10-10 | 李风宁 | Process for treating black digestion liquid generated by paper alkali pulping |
| CN1697901A (en) * | 2003-06-18 | 2005-11-16 | 玉米浆及纸制品公司 | Method for producing corn stalk pulp and paper products from corn stalk pulp |
Non-Patent Citations (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104032612A (en) * | 2014-06-17 | 2014-09-10 | 毛林涛 | Method for extracting lignin from alkaline straw pulp black liquor |
| CN105296568A (en) * | 2015-11-05 | 2016-02-03 | 中国科学院广州能源研究所 | Method for recycling alkali treatment lignocellulose waste fluid |
| CN105296568B (en) * | 2015-11-05 | 2019-03-08 | 中国科学院广州能源研究所 | A kind of method that alkali process lignocellulosic devil liquor recovery utilizes |
| CN105838756A (en) * | 2016-05-12 | 2016-08-10 | 中国科学院广州能源研究所 | Water-saving and emission-reduction technology for producing sugar through enzymolysis of lignocellulose treated with alkali |
| CN108048297A (en) * | 2017-11-20 | 2018-05-18 | 中国科学院广州能源研究所 | A kind of device applied to oxygenation pretreatment lignocellulosic enzymolysis saccharification water-saving and emission-reducing technique |
| WO2019095698A1 (en) * | 2017-11-20 | 2019-05-23 | 中国科学院广州能源研究所 | Device for water saving and emission reduction technology of alkali-pretreated lignocellulose enzymolysis and saccharification |
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Application publication date: 20111123 |