CN115418003A - Method for recovering lignin precipitate in strengthening alkali pretreatment liquid - Google Patents
Method for recovering lignin precipitate in strengthening alkali pretreatment liquid Download PDFInfo
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- CN115418003A CN115418003A CN202211284253.7A CN202211284253A CN115418003A CN 115418003 A CN115418003 A CN 115418003A CN 202211284253 A CN202211284253 A CN 202211284253A CN 115418003 A CN115418003 A CN 115418003A
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Abstract
The invention belongs to the technical field of lignocellulose biorefinery, and particularly relates to a method for recovering lignin precipitate in a strengthening alkali pretreatment solution, which comprises the following steps: adjusting the pH value of the alkali pretreatment solution to 4.8 by using acid, and centrifugally separating precipitate and clear liquid after the precipitate is separated out, wherein the obtained precipitate is crude lignin; the acid is water-soluble acid, and the alkali pretreatment liquid is liquid obtained after the lignocellulose biomass is pretreated by alkali or/and sulfite; adding a nonionic surfactant into the clear liquid, oscillating to form a suspension, standing for a period of time, centrifuging after precipitation, and recovering the precipitate, wherein the obtained precipitate is crude lignin. In the invention, a small amount of non-ionic surfactants such as tween, span or/and polyethylene glycol and the like are continuously added into the alkali pretreatment liquid so as to separate out more lignin and precipitate; meanwhile, the treated alkali pretreatment liquid can be directly used as enzymolysis liquid of an enzymolysis process in the production of cellulosic ethanol, so that the production cost of the lignocellulose biorefinery can be effectively reduced.
Description
Technical Field
The invention belongs to the technical field of lignocellulose biorefinery, and particularly relates to a method for recovering lignin precipitate in a strengthening alkali pretreatment solution.
Background
The large consumption of fossil energy causes a series of energy and environment problems such as unreasonable energy structure, large amount of CO2 emission and environmental deterioration, and the development and utilization of renewable energy are well appreciated at home and abroad. Under the background, lignocellulose which is the most abundant biomass resource on the earth at present enhances the energy development and utilization of the biomass resource, and is an effective measure for optimizing the energy structure and reducing CO2 emission in China.
Lignocellulose is mainly composed of cellulose, hemicellulose and lignin. Cellulose mainly plays a role of cytoskeleton, hemicellulose covers the surface of the cellulose to fill the gaps of the cellulose, and lignin and the hemicellulose can be connected through ether-ester bonds to form lignin-carbohydrate complexes (LCC) to mainly play a role of filling and bonding. The compact three-dimensional network structure enables the lignocellulose to have high degradation resistance. Therefore, the pretreatment method for destroying the compact structure of the lignocellulose to depolymerize and separate each component is a precondition for realizing the high-efficiency conversion and utilization of the lignocellulose, and determines the direction and efficiency of the subsequent lignocellulose biorefinery process.
Among the common biological, physical, chemical, physicochemical and comprehensive pretreatment methods, alkaline pretreatment has been widely used in the pulp and paper industry due to its advantages of mild reaction conditions, good lignin removal effects, etc., and is a very commercial technology for the refining process of lignocellulose such as cellulosic ethanol.
However, in alkaline pretreatment processes, large amounts of lignin-rich waste liquor are often produced, and this lignin is generally recovered by precipitation with acid. But the limited recovery results make the lignin waste under-utilized. Based on this, a simple, efficient and economical method for recovering lignin is needed.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for recovering lignin precipitate in a strengthening alkali pretreatment solution.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a method for recovering lignin precipitate in strengthening alkali pretreatment liquid comprises the following steps:
1) Adjusting the pH value of the alkali pretreatment solution to 4.8 by using acid, and centrifugally separating precipitate and clear liquid after the precipitate is separated out, wherein the obtained precipitate is crude lignin; the acid is water-soluble acid, and the alkali pretreatment liquid is liquid obtained after the lignocellulose biomass is pretreated by alkali or/and sulfite;
2) Adding a nonionic surfactant into the clear liquid obtained in the step 1), oscillating to form a turbid liquid, standing for a period of time, centrifuging after precipitation, and recovering the precipitate, wherein the obtained precipitate is crude lignin.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, in the step 1), the water-soluble acid is at least one of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, lactic acid and oxalic acid.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, in the step 1), the strong alkali is one of sodium hydroxide and potassium hydroxide.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, in the step 1), the sulfite is at least one of calcium sulfite, magnesium sulfite, sodium sulfite and ammonium sulfite.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, in step 1), the lignocellulose biomass is plants or wastes containing cellulose and lignin, including agricultural wastes, forestry wastes, energy plants and lignocellulose biorefinery wastes.
Further, according to the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, the lignocellulose biomass is at least one of pennisetum alopecuroides, poplar wood chips, walnut shells, corn straws, rice hulls and bagasse.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution as described above, in step 2), the nonionic surfactant is at least one of tween 20, tween 40, tween 60, tween 80, span 20, span 40, span 60, span 80, PEG1000, PEG1500, PEG2000, PEG4000, PEG6000, and PEG 8000.
Further, in the method for recovering lignin precipitate in the strengthening alkali pretreatment solution, the lignin precipitate is kept still for at least 10min in the step 2).
The invention has the beneficial effects that:
1. the pH value of the alkali pretreatment solution is firstly adjusted by acid to precipitate and separate part of lignin in the pretreatment solution, and then a small amount of nonionic surfactants such as Tween or/and span are continuously added into the alkali pretreatment solution to precipitate and separate out the lignin. Meanwhile, the treated alkali pretreatment solution can be directly used as enzymolysis solution of an enzymolysis process in the production of cellulosic ethanol, and the production cost of the lignocellulose biorefinery can be effectively reduced.
2. The method has scientific and reasonable design, and the method for strengthening lignin recovery by coupling the nonionic surfactant with the acid precipitation has the advantages of simple process and easy operation.
3. The nonionic surfactant used in the invention has low price and small dosage, and simultaneously, the lignin precipitation recovery effect is obviously improved, and the economic benefit is huge.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A method for recovering lignin precipitate in strengthening alkali pretreatment liquid comprises the following steps:
1) Adjusting the pH value of the alkali pretreatment solution to 4.8 by using acid, and centrifugally separating precipitate and clear liquid after the precipitate is separated out, wherein the obtained precipitate is crude lignin;
the acid is water-soluble acid, and the alkali pretreatment liquid is liquid obtained after the lignocellulose biomass is pretreated by alkali or/and sulfite;
2) Adding a nonionic surfactant into the clear liquid obtained in the step 1), oscillating to form a suspension, standing for at least 10min, centrifuging after precipitation, and recovering the precipitate to obtain crude lignin.
In the present invention, the water-soluble acid is at least one of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, lactic acid, and oxalic acid.
In the invention, the strong base is one of sodium hydroxide and potassium hydroxide.
In the invention, the sulfite is at least one of calcium sulfite, magnesium sulfite, sodium sulfite and ammonium sulfite.
In the invention, the lignocellulose biomass is plants or wastes containing cellulose and lignin, and the plants or wastes comprise agricultural wastes, forestry wastes, energy plants and lignocellulose biorefinery wastes. Specifically, the material can be at least one of pennisetum alopecuroides, poplar wood chips, walnut shells, corn stalks, rice hulls and bagasse.
In the invention, the nonionic surfactant is at least one of tween 20, tween 40, tween 60, tween 80, span 20, span 40, span 60, span 80, PEG1000, PEG1500, PEG2000, PEG4000, PEG6000 and PEG 8000.
The following embodiments are relevant to the present invention:
the alkali pretreatment liquids used in the comparative examples and examples were liquids obtained after strongly alkali pretreatment of lignocellulosic biomass. The strong base is sodium hydroxide, the lignocellulose biomass is walnut shells, and the addition amount of the strong base is 4% of the mass of the lignocellulose biomass.
Comparative example
In the comparative example, only acetic acid was added to precipitate and separate lignin from the alkali pretreatment solution.
Acetic acid was added dropwise to 10mL of the alkali pretreatment solution (lignin concentration: about 10 mg/mL) at room temperature until the pH of the pretreatment solution became 4.8, the mixture was shaken and mixed, and then left to stand for 10min, followed by centrifugation (1955 g. Times.2 min) to separate the precipitate and the supernatant, and the lignin recovery rate was 67%.
Example 1
Adding acetic acid dropwise into 10mL of alkali pretreatment solution (lignin concentration is about 10 mg/mL) at room temperature until pH of the pretreatment solution is 4.8, shaking, standing for 10min, and centrifuging (1955 g × 2 min) to separate precipitate and supernatant; then, 4% Tween 20 was added to the obtained supernatant in a mass-to-volume ratio (w/v, g/mL), the mixture was shaken and mixed, and then allowed to stand for 10min, and the precipitate and the supernatant were separated by centrifugation (1955 g. Times.2 min), whereby the lignin recovery rate was 81%.
Compared with the comparative example, the addition of 4% tween 20 can significantly improve the recovery rate of lignin.
Example 2
Adding acetic acid dropwise into 10mL of alkali pretreatment solution (lignin concentration is about 10 mg/mL) at room temperature until pH of the pretreatment solution is 4.8, shaking, standing for 10min, and centrifuging (1955 g × 2 min) to separate precipitate and supernatant; then, 5% Tween 20 was added to the obtained supernatant in a mass-to-volume ratio (w/v, g/mL), the mixture was shaken and mixed, and then allowed to stand for 10min, and the precipitate and the supernatant were separated by centrifugation (1955 g. Times.2 min), whereby the lignin recovery rate was 82%.
Compared with the comparative example, the addition of 5% of tween 20 can obviously improve the recovery rate of lignin.
Example 3
Adding acetic acid dropwise into 10mL of alkali pretreatment solution (lignin concentration is about 10 mg/mL) at room temperature until pH of the pretreatment solution is 4.8, shaking, standing for 10min, and centrifuging (1955 g × 2 min) to separate precipitate and supernatant; then, 8% Tween 20 was added to the obtained supernatant in a mass-to-volume ratio (w/v, g/mL), the mixture was shaken and mixed, and then allowed to stand for 10min, and the precipitate and the supernatant were separated by centrifugation (1955 g. Times.2 min), whereby the lignin recovery rate was 77%.
Compared with the comparative example, the addition of 8% of tween 20 can significantly improve the lignin recovery rate.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A method for recovering lignin precipitate in strengthening alkali pretreatment liquid is characterized by comprising the following steps:
1) Adjusting the pH value of the alkali pretreatment solution to 4.8 by using acid, and centrifugally separating precipitate and clear liquid after the precipitate is separated out, wherein the obtained precipitate is crude lignin; the acid is water-soluble acid, and the alkali pretreatment liquid is liquid obtained after the lignocellulose biomass is pretreated by alkali or/and sulfite;
2) Adding a nonionic surfactant into the clear liquid obtained in the step 1), oscillating to form a turbid liquid, standing for a period of time, centrifuging after precipitation, and recovering the precipitate, wherein the obtained precipitate is crude lignin.
2. The method for recovering lignin precipitate in the enhanced alkali pretreatment liquor according to claim 1, wherein: in the step 1), the water-soluble acid is at least one of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, lactic acid and oxalic acid.
3. The method for recovering lignin precipitate in the enhanced alkali pretreatment liquor according to claim 1, wherein: in the step 1), the strong base is one of sodium hydroxide and potassium hydroxide.
4. The method for recovering lignin precipitate in the enhanced alkali pretreatment liquor according to claim 1, wherein: in the step 1), the sulfite is at least one of calcium sulfite, magnesium sulfite, sodium sulfite and ammonium sulfite.
5. The method for recovering lignin precipitate in the strengthening alkali pretreatment solution as recited in claim 1, wherein: in the step 1), the lignocellulose biomass is plants or wastes containing cellulose and lignin, including agricultural wastes, forestry wastes, energy plants and lignocellulose biorefinery wastes.
6. The method for precipitation recovery of lignin from the strengthening alkali pretreatment liquid according to claim 5, wherein the lignocellulosic biomass is at least one of pennisetum, poplar wood chips, walnut shells, corn stover, rice hulls, and bagasse.
7. The method for recovering lignin precipitate in the strengthening alkali pretreatment solution as recited in claim 1, wherein: in the step 2), the non-ionic surfactant is at least one of tween 20, tween 40, tween 60, tween 80, span 20, span 40, span 60, span 80, PEG1000, PEG1500, PEG2000, PEG4000, PEG6000 and PEG 8000.
8. The method for recovering lignin precipitate in the strengthening alkali pretreatment liquid according to claim 1, wherein in the step 2), standing is carried out for at least 10min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115819796A (en) * | 2022-12-29 | 2023-03-21 | 浙江科技学院 | Method for efficiently separating organic acid lignin |
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