CN108265540A - A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass - Google Patents
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass Download PDFInfo
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- CN108265540A CN108265540A CN201810179565.9A CN201810179565A CN108265540A CN 108265540 A CN108265540 A CN 108265540A CN 201810179565 A CN201810179565 A CN 201810179565A CN 108265540 A CN108265540 A CN 108265540A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/02—Pretreatment of the raw materials by chemical or physical means
- D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
Abstract
The present invention provides a kind of methods of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, include the following steps：(1) it pre-processes：Biomass material is handled after crushing, being sieved with liquid nitrogen, then carries out hydro-thermal process, and the solid-to-liquid ratio of hydro-thermal process is 1:3~8 (g/mL), hydrothermal temperature are 150~250 DEG C, and the hydro-thermal time is 1~6h；(2) it extracts：Material after pretreatment is by extracting, filtering and obtaining filter residue and supernatant；It is centrifuged after supernatant tune pH value, gained sediment is through dry that lignin, filter residue are digested；Addition of the method for the present invention without acid-base reagent, low to the original structure extent of the destruction of lignin, hydro-thermal can also effectively remove hemicellulose, and hydrothermal pretreatment is coupled using liquid nitrogen cryogenics, the extraction efficiency to lignin from biomass is improved, while increases the DNA purity of lignin.
Description
Technical field
The present invention relates to lignin extraction technical fields, and in particular to a kind of liquid nitrogen coupling hydrothermal pretreatment extraction biomass
The method of middle lignin.
Background technology
With the increasingly depleted of fossil resources, fossil resources are substituted with reproducible biomass resource, pass through biorefinery
It is research hotspot and solution the present in a very long time from now on that technology, which converts biomass into the energy, chemicals and material,
The inevitable means of human environment, resource and energy problem afterwards.In the technological process of resource conversion, the pretreatment of biomass occupies
Critical role, the extracts reagent of efficient preprocess method meeting let us is more convenient and thorough to the component progress in biomass
The separation at bottom so that subsequent technological process is easier, efficient, and has to the quality and condition of follow-up chemicals obtained
Great influence.
The preprocess method of biomass can substantially be divided at present：The pre- place of physics pretreatment, Chemical Pretreatment, biology
Reason.Traditional preprocess method is larger to the destruction of wood fibre, and separation degree is uneven, the wood fibre purity extracted
Difference, various wood fibres mutually adulterate.The shortcomings that in order to overcome single preprocess method, gives full play to various preprocess methods certainly
The advantage of body, the method for developing various combination pretreatments successively.But existing mixed processing method does not reach ideal yet
Effect, greatest problem are of high cost, and equipment requirement is high, and continuous production can not be reached, and the addition of soda acid or ammonia consumption cause
The surge of cost, recycling problem can not be solved effectively.
Invention content
The purpose of the present invention is to provide a kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, nothings
The addition of acid-base reagent, low to the original structure extent of the destruction of lignin, hydro-thermal can also effectively remove hemicellulose, utilize liquid nitrogen
Low temperature couples hydrothermal pretreatment, improves the extraction efficiency to lignin from biomass, while increase the DNA purity of lignin.
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, includes the following steps：
(1) it pre-processes：Biomass material is handled after crushing, being sieved with liquid nitrogen, then carries out hydro-thermal process, hydro-thermal process
Solid-to-liquid ratio is 1:3~8 (g/mL), hydrothermal temperature are 150~250 DEG C, and the hydro-thermal time is 1~6h；
(2) it extracts：Material after pretreatment is by extracting, filtering and obtaining filter residue and supernatant；After supernatant tune pH value from
The heart, gained sediment is through dry that lignin, filter residue are digested.
Preferably, the dip time of the liquid nitrogen processing is 0.5~20min, and dipping time is 1~10 time.
Preferably, the extraction solvent is one kind in organic solvent, depth congruent melting solvent, ionic liquid；It is described organic
Solvent is ethylene glycol, one kind in 1,4- butanediols, acetone, methanol；The depth congruent melting solvent is with lewis acid or height boiling
Alcohol is the depth congruent melting solvent of hydrogen bond donor；The ionic liquid is 1- ethyl-3-methylimidazoles acetate or 1- propyl -3- first
Base imidazoleacetic acid salt.
Preferably, the extraction solvent is organic solvent, and extraction time is 60~180min, and extraction temperature is 140~180
DEG C, solid-to-liquid ratio 1:5~20 (g/mL).
Preferably, the extraction solvent is depth congruent melting solvent, and extraction time is 60~240min, extraction temperature for 10~
90 DEG C, solid-to-liquid ratio 1:1~15 (g/mL).
Preferably, the extraction solvent is ionic liquid, and extraction time is 60~240min, and extraction temperature is 120~180
DEG C, solid-to-liquid ratio 1:1~15 (g/mL).
Preferably, the biomass smashes it through 20~100 mesh sieve.
Preferably, the biomass material is a kind of in following substance or at least two mixture：Maize straw,
Rice straw, wheat stalk, beanstalk, broomcorn straw；Clover, hybrid giant napier；Wood shavings, sawdust, twig；Energy-source plant awns
Grass, switchgrass, fast-growing willow each section；Shell, fruit stone.
The beneficial effects of the invention are as follows：
The method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass of the present invention.Liquid nitrogen is easy to use, operates ratio
It is relatively simple, laboratory equipment is required than relatively low；Sample can make water be in glassy state under low-temperature condition by liquid nitrogen fast freezing,
The generation of ice crystal is reduced, and the crystallinity of stalk can be reduced, the structure of sample itself is not influenced, remains wood fibre higher
Natural structure, and hydro-thermal process is considered as to effectively remove the processing method of hemicellulose in sample always, by both
The pretreatment of method coupling and then the extraction plus more mild extraction reagent so that the extraction of lignin from biomass
Efficiency and purity are obviously improved.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention,
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
All other embodiments obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment 1：
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, includes the following steps：
(1) it pre-processes：Birch sawdust crosses 20 mesh sieve, the original that 100g is taken to be pre-processed as liquid nitrogen cryogenics after crushing
Material；Drying is immersed in liquid nitrogen, dip time 2min, and dipping time is 5 times；Then hydro-thermal process is carried out, hydro-thermal process is consolidated
Liquor ratio is 1:4 (g/mL), hydrothermal temperature are 170 DEG C, and the hydro-thermal time is 1h；
(2) it extracts：Material after pretreatment is put into 200ml reaction kettles, uses 30% concentration (volumetric concentration)
1,4-butanediol is extracted, solid-to-liquid ratio 1:6 (g/mL), extraction temperature are 150 DEG C, extraction time 120min；It depressurized
Filter, supernatant with 2mol/L salt acid for adjusting pH to 4 when centrifuged, gained sediment drying after lignin.
Through component analysis, the results showed that gained lignin purity is 93%, and lignin extraction rate is 53%；After filtering
Filter residue is digested, and compared with untreated birch sawdust, enzymatic hydrolyzation improves 42%.
Embodiment 2：
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, includes the following steps：
(1) it pre-processes：Maize straw crosses 30 mesh sieve, the original that 100g is taken to be pre-processed as liquid nitrogen cryogenics after crushing
Material；Drying is immersed in liquid nitrogen, dip time 13min, and dipping time is 3 times；Then hydro-thermal process is carried out, hydro-thermal process
Solid-to-liquid ratio is 1:5 (g/mL), hydrothermal temperature are 180 DEG C, and the hydro-thermal time is 2h；
(2) it extracts：Material after pretreatment is put into 200ml reaction kettles, uses the 1,4-butanediol of 50% concentration
It is extracted, solid-to-liquid ratio 1:10 (g/mL), extraction temperature are 160 DEG C, extraction time 180min；It is filtered under diminished pressure, supernatant
It is centrifuged during with 2mol/L salt acid for adjusting pH to 4, lignin is obtained after the drying of gained sediment.
Through component analysis, the results showed that gained lignin purity is 93%, and lignin extraction rate is 53%；After filtering
Filter residue is digested, and compared with untreated maize straw, enzymatic hydrolyzation improves 51%.
Embodiment 3：
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, includes the following steps：
(1) it pre-processes：Walnut shell crosses 60 mesh sieve, the raw material that 100g is taken to be pre-processed as liquid nitrogen cryogenics after crushing；
Drying is immersed in liquid nitrogen, dip time 10min, and dipping time is 8 times；Then hydro-thermal process, the solid-liquid of hydro-thermal process are carried out
Than being 1:6 (g/mL), temperature are 180 DEG C, processing time 4h；
(2) it extracts：Material after pretreatment is used into choline chloride/boric acid (3:5) the depth congruent melting solvent of combination
(DES) it is extracted, solid-to-liquid ratio 1:5 (g/mL), 120min is extracted under the conditions of 90 DEG C；It is filtered under diminished pressure, supernatant 2mol/
It is centrifuged when L salt acid for adjusting pH is to 4, lignin is obtained after the drying of gained sediment.
Through component analysis, the results showed that gained lignin purity is 95%, and lignin extraction rate is 57%；After filtering
Filter residue is digested, and compared with untreated walnut shell, enzymatic hydrolyzation improves 44%.
Embodiment 4：
A kind of method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, includes the following steps：
(1) it pre-processes：Chinese silvergrass sieves with 100 mesh sieve after crushing, the raw material that 100g is taken to be pre-processed as liquid nitrogen cryogenics；It dries
It is dry, it immerses in liquid nitrogen, dip time 5min, dipping time is 7 times；Then hydro-thermal process, the solid-to-liquid ratio of hydro-thermal process are carried out
It is 1:7 (g/mL), temperature are 210 DEG C, processing time 5h；
(2)) it extracts：Material after pretreatment is soaked using 1- propyl -3- N-Methylimidazoleacetic ionic liquids
It carries, solid-to-liquid ratio 1:6 (g/mL), extraction temperature are 140 DEG C, and extraction time 120min is filtered under diminished pressure, supernatant 2mol/L
It is centrifuged when salt acid for adjusting pH is to 4, lignin is obtained after the drying of gained sediment.
Through component analysis, the results showed that gained lignin purity is 94%, and lignin extraction rate is 58%；After filtering
Filter residue is digested, and compared with untreated Chinese silvergrass, enzymatic hydrolyzation improves 45%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to aforementioned each implementation
Technical solution recorded in example modifies or carries out equivalent replacement to which part technical characteristic；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (8)
- A kind of 1. method of liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass, which is characterized in that include the following steps：(1) it pre-processes：Biomass material is handled after crushing, being sieved with liquid nitrogen, then carries out hydro-thermal process, the solid-liquid of hydro-thermal process Than being 1:3~8 (g/mL), hydrothermal temperature are 150~250 DEG C, and the hydro-thermal time is 1~6h；(2) it extracts：Material after pretreatment is by extracting, filtering and obtaining filter residue and supernatant；It is centrifuged after supernatant tune pH value, institute Sediment is obtained through dry that lignin, filter residue are digested.
- 2. the method for liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass according to claim 1, feature exist In the dip time of the liquid nitrogen processing is 0.5~20min, and dipping time is 1~10 time.
- 3. the method for liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass according to claim 1, feature exist In the extraction solvent is organic solvent, one kind in depth congruent melting solvent, ionic liquid；The organic solvent for ethylene glycol, One kind in 1,4- butanediols, acetone, methanol；The depth congruent melting solvent is using lewis acid or high boiling alcohol as hydrogen bond donor Depth congruent melting solvent；The ionic liquid is 1- ethyl-3-methylimidazoles acetate or 1- propyl -3- N-Methylimidazoleacetic salt.
- 4. the method for liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass according to claim 3, feature exist In the extraction solvent is organic solvent, and extraction time is 60~180min, and extraction temperature is 140~180 DEG C, and solid-to-liquid ratio is 1:5~20 (g/mL).
- 5. the method for liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass according to claim 3, feature exist In the extraction solvent is depth congruent melting solvent, and extraction time is 60~240min, and extraction temperature is 10~90 DEG C, solid-to-liquid ratio It is 1:1~15 (g/mL).
- 6. the method for liquid nitrogen coupling hydrothermal pretreatment extraction lignin from biomass according to claim 3, feature exist In the extraction solvent is ionic liquid, and extraction time is 60~240min, and extraction temperature is 120~180 DEG C, and solid-to-liquid ratio is 1:1~15 (g/mL).
- 7. the method for hydrothermal pretreatment extraction lignin from biomass is coupled according to claim 1-6 any one of them liquid nitrogen, It is characterized in that, the biomass smashes it through 20~100 mesh sieve.
- 8. the method for hydrothermal pretreatment extraction lignin from biomass is coupled according to claim 1-6 any one of them liquid nitrogen, It is characterized in that, the biomass material is a kind of in following substance or at least two mixture：Maize straw, rice Stalk, wheat stalk, beanstalk, broomcorn straw；Clover, hybrid giant napier；Wood shavings, sawdust, twig；Energy-source plant Chinese silvergrass, willow Branch millet, each section of fast-growing willow；Shell, fruit stone.
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Cited By (2)
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| CN109322201A (en) * | 2018-09-20 | 2019-02-12 | 上海同化新材料科技有限公司 | A kind of cellulose pyrolysis purifying extrusion device and the purification process based on the device |
| CN111961220A (en) * | 2020-08-21 | 2020-11-20 | 齐鲁工业大学 | Method for efficiently separating straw components by adopting novel eutectic solvent |
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Application publication date: 20180710 |