CN110563972A - Novel biomass-based solvent, preparation method and application thereof - Google Patents
Novel biomass-based solvent, preparation method and application thereof Download PDFInfo
- Publication number
- CN110563972A CN110563972A CN201810567535.5A CN201810567535A CN110563972A CN 110563972 A CN110563972 A CN 110563972A CN 201810567535 A CN201810567535 A CN 201810567535A CN 110563972 A CN110563972 A CN 110563972A
- Authority
- CN
- China
- Prior art keywords
- biomass
- cellulose
- based solvent
- solvent
- methylmorpholine
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Abstract
The application discloses a novel biomass-based solvent, which comprises a polyhydroxy-containing compound and N-methylmorpholine-N-oxide; wherein the mass ratio of the polyhydroxy-containing compound to the N-methylmorpholine-N-oxide is 3: 1-1: 3. The solvent has the advantages of good fluidity, stable chemical property, safety, recycling, environmental protection and the like, has strong dissolving capacity on cellulose, can dissolve the cellulose at a relatively low temperature (80-150 ℃) and obtain a cellulose solution with high quality fraction (10-35.5%). The application also discloses a preparation method and application of the compound, and the method has the advantages of cheap and easily-obtained raw materials, simplicity and high efficiency.
Description
Technical Field
The application relates to a novel biomass-based solvent, a preparation method and application thereof, and belongs to the fields of green chemistry, biomass chemistry, spinning and the like.
Background
With the increasing shortage of fossil resources, the resource utilization of renewable biomass has become a research hotspot concerned globally. Cellulose is a biomass resource with abundant reserves in the nature, but natural cellulose molecules contain a large amount of hydroxyl groups, and the structure contains a large amount of intermolecular and intramolecular hydrogen bonds to form a complex hydrogen bond network structure, so that the cellulose is difficult to dissolve in water, ethanol and most of organic solvents, has poor processing performance, and seriously hinders the application in the utilization processes of further spinning, chemical conversion and the like. Therefore, an efficient cellulose dissolving system is found, and the method has important significance for overcoming the defects of difficult dissolution, difficult modification, non-plasticity and the like of cellulose.
Currently, cellulose solvents mainly include the following three types: water-soluble solvents, ionic liquids, and eutectic solvents. Among them, typical examples of the water-soluble solvent are copper ammonia solution and copper-ethylenediamine solution, and these metal complex aqueous solutions cause metal ion pollution in water when discharged, and it is difficult to meet increasingly strict environmental protection requirements. Another common water-soluble solvent for cellulose is NMMO/water, patent No. US2179181, which requires a complicated evaporation and concentration apparatus for dissolving cellulose, and has high energy consumption, complicated operation, and strict requirements on water content, and when the water content is higher than a certain ratio, cellulose can only swell and cannot be dissolved. Meanwhile, the solvent has high viscosity, and needs to meet specific operating conditions in the using process.
Ionic liquids, which are good cellulose solvents with low melting points, are patent No. CN201410404512.4, but require pretreatment of cellulose with acid-base solutions, and most of them contain halogen anions, causing corrosion to equipment and also having the disadvantage of environmental pollution; meanwhile, the ionic liquid has complex synthesis steps, high cost and difficult recovery, and is not beneficial to large-scale industrial production and application.
The eutectic solvent is a novel solvent developed in recent years, and the property of the eutectic solvent is similar to that of an ionic liquid. Generally, the catalyst consists of two components, wherein the first component is a hydrogen bond receptor and generally adopts quaternary ammonium salt; the second component is a hydrogen bond donor, typically an organic carboxylic acid, organic alcohol or amide compound. However, in the eutectic solvents, choline chloride is mainly adopted as the quaternary ammonium salt, chloride ions have pollution and corrosion, the requirement on equipment is high, the production cost is greatly increased, and the problem that large-scale production cannot be realized is also existed.
In summary, there is a need to develop a novel cellulose solvent, which has the characteristics of environmental protection, easy availability of raw material source, good solubility to cellulose, liquid at room temperature, appropriate viscosity, easy subsequent processing, and easy preparation. The development of novel cellulose solvents is necessary and has important industrial application value.
Disclosure of Invention
According to one aspect of the application, the biomass-based solvent is good in mobility, stable in chemical property, safe, recyclable, green and environment-friendly and the like, has strong dissolving capacity for cellulose, is liquid at room temperature, has proper viscosity and is beneficial to subsequent processing and application.
The biomass-based solvent comprises a polyhydroxy-containing compound and N-methylmorpholine-N-oxide;
Wherein the mass ratio of the polyhydroxy-containing compound to the N-methylmorpholine-N-oxide is 3: 1-1: 3.
Optionally, the polyhydroxy-containing compound comprises at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, sorbitol, xylitol, glucose, isosorbide, isoidide, isomannide.
According to another aspect of the application, a preparation method of the biomass-based solvent is provided, the method is safe and environment-friendly, raw materials comprise biomass-based sources, the raw materials are cheap and easy to obtain, and the preparation method is simple and efficient.
The method comprises the steps of mutually dissolving a polyhydroxy-containing compound and N-methylmorpholine-N-oxide to prepare a biomass-based solvent;
The mass ratio of the polyhydroxy-containing compound to the N-methylmorpholine-N-oxide is 3: 1-1: 3.
Alternatively, the lower limit of the mass ratio of the polyhydroxy-containing compound to N-methylmorpholine-N-oxide may be independently selected from 3:1, 2.5:1, 2:1, 1.5:1, 1:1.5, 1:2, 1:2.5, 1:3, and any point in the range consisting of any two of the above.
Alternatively, the upper limit of the mass ratio of the polyhydroxy-containing compound to N-methylmorpholine-N-oxide may be independently selected from 3:1, 2.5:1, 2:1, 1.5:1, 1:1.5, 1:2, 1:2.5, 1:3, and any point in the range consisting of any two of the above.
Optionally, the polyhydroxy-containing compound is a biomass polyhydroxy compound.
Optionally, the polyhydroxy-containing compound and the N-methylmorpholine-N-oxide are weighed in proportion, heated to 30-100 ℃, stirred to be completely miscible, and cooled to room temperature to obtain the biomass-based solvent.
Optionally, the upper limit of the heating temperature is selected from 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the lower limit is selected from 30 deg.C, 40 deg.C, 50 deg.C or 60 deg.C.
Optionally, the polyhydroxy-containing compound and the N-methylmorpholine-N-oxide are weighed in proportion, heated to 70-100 ℃, stirred to be completely miscible, and cooled to room temperature to obtain the biomass-based solvent.
Optionally, the stirring time is 5-40 min.
The method utilizes the hydrogen bond effect to design and prepare a novel chlorine-free solvent which takes N-methylmorpholine-N-oxide as a hydrogen bond acceptor and a biomass polyhydroxy compound as a hydrogen bond donor.
By "biomass-based polyhydroxyl compound" is meant herein a polyhydroxyl compound derived from biomass.
Weighing a certain amount of polyhydroxy compounds including ethylene glycol, glycerol, isosorbide, xylitol, 1, 2-propylene glycol, 1, 3-propylene glycol, glucose, isoidide and isomannide, adding N-methylmorpholine-N-oxide in a certain proportion, heating to 30-100 ℃, stirring until mutual solubility is achieved, and cooling to room temperature to obtain a biomass-based solvent; adding a certain proportion of cellulose into the obtained biomass-based solvent, heating to 80-150 ℃, keeping the temperature for a certain time at a constant temperature, and fully dissolving the cellulose to obtain a cellulose solution, wherein the mass fraction of the cellulose is 10-35.5%.
According to yet another aspect of the present application, there is provided a cellulosic solvent characterized by comprising at least one of any of the biomass-based solvents described above, produced according to any of the methods described above.
According to a further aspect of the present application, there is provided the use of the above-described cellulose solvent for dissolving cellulose. The cellulose solvent can be used as a green solvent for replacing a volatile organic solvent to dissolve cellulose, and has strong dissolving capacity for the cellulose at a relatively low temperature.
Optionally, adding cellulose into the cellulose solvent, heating to a dissolving temperature and keeping for a set time, and stirring to obtain a cellulose transparent solution.
Optionally, the degree of polymerization of the cellulose is 300 to 1500.
Optionally, the cellulose comprises at least one of alpha-cellulose powder, cotton pulp cellulose, cellulose filter paper, or microcrystalline cellulose.
Optionally, the dissolving temperature is 80-150 ℃, and the set time is 10-90 min;
The mass fraction of the cellulose transparent solution is 10-35.5%.
Optionally, the dissolving temperature is 120-150 ℃, and the set time is 30-90 min.
Alternatively, the lower dissolution temperature limit may be independently selected from 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, and any point in a range consisting of any two of the above points.
Alternatively, the upper dissolution temperature limit may be independently selected from 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, and any point in a range consisting of any two of the above points.
In the application, the biomass-based solvent has the best dissolving performance on cellulose at the temperature of 80-150 ℃.
Benefits that can be produced by the present application include, but are not limited to:
1) The preparation method of the biomass-based solvent has the advantages of safety, high efficiency, environmental friendliness and the like, and the raw materials are cheap and easy to obtain, and the preparation method is simple.
2) According to the biomass-based solvent prepared by the method, the hydrogen bond acceptor does not contain halogen ions such as chlorine ions, and the hydrogen bond donor is derived from a biomass-based polyhydroxy compound and can be used as a green solvent for replacing a volatile organic solvent to dissolve cellulose.
3) The biomass-based solvent prepared by the method provided by the application has good fluidity and stable chemical property, can be recycled, and has strong dissolving capacity for cellulose at relatively low temperature.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, wherein the polyhydroxy-containing compound was purchased from Shanghai Aladdin Biotech, Inc.; N-methylmorpholine-N-oxide is available from Shanghai ai-Exhibit chemical science and technology, Inc.
In the present application, the mass fraction of the cellulose solution is analyzed and calculated using an abbe refractometer.
Example 1 preparation of Biomass based solvent
1#Preparation of biomass-based solvents
Weighing 5g of ethylene glycol and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 30 ℃, stirring for 40min until the two solids are completely mutually soluble to obtain a yellowish solution, which is marked as 1#a biomass-based solvent.
Will 1#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 2.4X 10 as measured with a digital viscometer-3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
2#Preparation of biomass-based solvents
10g of ethylene glycol and 15g N-methylmorpholine N-oxide were weighed into a 100mL round bottom flask, heated to 90 ℃ in an oil bath and stirred for 10min until the two solids are completely mutually soluble to obtain a yellowish solution, which is marked as 2#A biomass-based solvent.
Will 2#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 2.0X 10 as measured with a digital viscometer-3pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
3#Preparation of biomass-based solvents
Weighing 15g of ethylene glycol and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 100 ℃, stirring for 5min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 3#A biomass-based solvent.
Will 3#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 1.8X 10 as measured with a digital viscometer-3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
4#Preparation of biomass-based solvents
15g of ethylene glycol and 10g N-methylmorpholine-N-oxide are weighed in a 100mL round bottom flask, heated to 40 ℃ in an oil bath, stirred for 30min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 4#A biomass-based solvent.
Will 4#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 1.6X 10 as measured with a digital viscometer-3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
5#preparation of biomass-based solvents
Weighing 10g of ethylene glycol and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 50 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 5#A biomass-based solvent.
Will 5#Cooling the biomass-based solvent to 20 deg.C, and measuring with digital viscometerThe viscosity of the solvent was 2.0X 10-3pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
6#Preparation of biomass-based solvents
Weighing 15g of isosorbide and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 70 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 6#A biomass-based solvent.
Will 6#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 26.4X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the isosorbide is not oxidized, and the chemical property is stable.
7#Preparation of biomass-based solvents
Weighing 15g of xylitol and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 80 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 7#A biomass-based solvent.
Will 7#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 12.4X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the xylitol is not oxidized, and the chemical property is stable.
8#Preparation of biomass-based solvents
Weighing 10g of 1, 3-propylene glycol and 10g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 60 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 8#A biomass-based solvent.
Will 8#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 6.1X 10 as measured with a digital viscometer-3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled and volatilized, the 1, 3-propylene glycol is not oxidized, and the chemical property is stable。
9#Preparation of biomass-based solvents
weighing 10g of glycerol and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 80 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 9#A biomass-based solvent.
Will 9#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 16.2X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycerol is not oxidized, and the chemical property is stable.
10#Preparation of biomass-based solvents
Weighing 10g of glucose and 10g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 100 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 10#A biomass-based solvent.
Will 10#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 32.3X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glucose is not oxidized, and the chemical property is stable.
11#Preparation of biomass-based solvents
Weighing 15g of isoidide and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 80 ℃, stirring for 20min until the two solids are completely mutually soluble to obtain a yellowish solution, which is recorded as 11#A biomass-based solvent.
Will 11#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was measured to be 25.2X 10 using a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the isoidide is not oxidized, and the chemical property is stable.
12#Preparation of biomass-based solvents
In a 100mL round bottom flask, 15g of isomannide was weighedAnd 15g N-methylmorpholine-N-oxide, heating to 80 deg.C in oil bath, stirring for 20min until the two solids are completely dissolved to obtain yellowish solution 12#A biomass-based solvent.
Will 12#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was measured to be 25.4X 10 using a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the glycol is not oxidized, and the chemical property is stable.
13#Preparation of biomass-based solvents
Weighing 5g of isosorbide, 5g of isomannide, 5g of isoidide and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating in an oil bath to 80 ℃, stirring for 30min until the two solids are completely mutually dissolved to obtain a yellowish solution, which is marked as 13#A biomass-based solvent.
Will 13#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 31.4X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, the isosorbide, the isomannide and the isoidide are not oxidized, and the chemical property is stable.
14#Preparation of biomass-based solvents
Weighing 5g of sorbitol, 5g of isosorbide and 15g N-methylmorpholine-N-oxide in a 100mL round bottom flask, heating the mixture in an oil bath to 80 ℃, stirring the mixture for 20min until the two solids are completely mutually dissolved to obtain a yellowish solution, which is recorded as 14#A biomass-based solvent.
Will 14#The biomass-based solvent was cooled to 20 ℃ and the resulting solvent viscosity was 38.2X 10 as measured with a digital viscometer- 3Pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, sorbitol and isosorbide are not oxidized, and the chemical property is stable.
15#Preparation of biomass-based solvents
In a 100mL round bottom flask, 2g xylitol, 3g glucose and 15g N-methylmorpholine-N-oxide were weighed in an oil bathHeating to 80 deg.C, stirring for 20min until the two solids are completely dissolved to obtain yellowish solution, which is recorded as 15#A biomass-based solvent.
Will 15#The biomass-based solvent is cooled to 20 ℃, and the viscosity of the obtained solvent is 42.1 multiplied by 10-3pa.s, good fluidity; the temperature is raised to 150 ℃, the biomass-based solvent is not boiled, the solvent is not volatilized, neither xylitol nor glucose is oxidized, and the chemical property is stable.
Example 2 use of Biomass-based solvent for dissolving cellulose
As 1 prepared in example 1#～15#The biomass-based solvent is a solvent for dissolving cellulose.
To the direction of1#Biomass-based solventAdding inAlpha-cellulose powder10g (with the polymerization degree of 1500), heating to 140 ℃, stirring for 90min until cellulose is completely dissolved to obtain a yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 33.3%, washing and filtering the obtained solution to obtain a lower clear solution, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the cellulose-cellulose composite material1#Biomass based solvent recovery of about 98％，1#The biomass-based solvent can be recycled。
To the direction of1#Biomass-based solventAdding inCotton pulp cellulose11g (the polymerization degree is 1000), heating to 120 ℃, stirring for 70min until the cotton pulp cellulose is completely dissolved to obtain a yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 35.5%.
To the direction of1#Biomass-based solventAdding inCellulose filter paper11g (the polymerization degree is 700), heating to 90 ℃, stirring for 80min until the cellulose filter paper is completely dissolved to obtain a yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 35.5%.
To the direction of1#Biomass-based solventAdding inMicrocrystalline cellulose11g (the polymerization degree is 300), heating to 80 ℃, stirring for 20min until the microcrystalline cellulose is completely dissolved to obtain a yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 35.5%.
To the direction of5#Biomass-based solventAdding inα-Cellulose powder10g (with the polymerization degree of 1500), heating to 100 ℃, stirring for 30min until the cellulose powder is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 28.6%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the final product5#Biomass based solvent recovery of about 98％，5#The biomass-based solvent can be recycled。
To the direction of6#Biomass-based solventAdding inAlpha-cellulose powder5g (the polymerization degree is 1500), heating to 110 ℃, stirring for 40min until the cellulose powder is completely dissolved to obtain a dark yellow transparent solution, wherein the mass fraction of the cellulose in the solution is 14.3%, washing and filtering the obtained solution to obtain a lower clear solution, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the cellulose acetate6#Biomass based solvent with a recovery of about 99％，6#The biomass-based solvent can be recycled。
To the direction of7#Biomass-based solventAdding inMicrocrystalline cellulose5g (the polymerization degree is 300), heating to 150 ℃, stirring for 10min until the microcrystalline cellulose is completely dissolved to obtain a dark yellow transparent solution, wherein the mass fraction of the cellulose in the solution is 14.3%, washing and filtering the obtained solution to obtain a lower clear solution, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the final product7#Biomass based solvent with a recovery of about 99％，7#the biomass-based solvent can be recycled。
To the direction of8#Biomass-based solventAdding inCellulose filter paper5g (the polymerization degree is 700), heating to 140 ℃, stirring for 60min until the cellulose filter paper is completely dissolved to obtain a dark yellow transparent solution, wherein the mass fraction of the cellulose in the solution is 20%, washing and filtering the obtained solution to obtain a lower clear solution, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ in a vacuum drying oven to obtain the cellulose acetate8#Biomass based solvent with a recovery of about 99％，8#The biomass-based solvent can be recycled。
To the direction of9#Biomass-based solventAdding inMicrocrystalline cellulose powder10g (the polymerization degree is 300), heating to 140 ℃, stirring for 60min until the microcrystalline cellulose is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 28.6%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the microcrystalline cellulose9#Biomass based solvent with a recovery of about 99％，9#The biomass-based solvent can be recycled。
To the direction of10#Biomass-based solventAdding inMicrocrystalline cellulose powder6g (the polymerization degree is 300), heating to 120 ℃, stirring for 90min until the microcrystalline cellulose is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 23.1%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the microcrystalline cellulose10#Biomass based solvent with a recovery of about 99％，10#The biomass-based solvent can be recycled。
To the direction of11#Biomass-based solventAdding inMicrocrystalline cellulose4g (the polymerization degree is 300), heating to 130 ℃, stirring for 50min until the microcrystalline cellulose is completely dissolved to obtain a dark yellow transparent solution, wherein the mass fraction of the cellulose in the solution is 11.8%, washing and filtering the obtained solution to obtain a lower clear solution, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the final product11#Biomass based solvent with a recovery of about 99％，11#The biomass-based solvent can be recycled。
To the direction of12#Biomass-based solventAdding inCotton pulp cellulose6g (with the polymerization degree of 1000), heating to 140 ℃, stirring for 60min until the cotton pulp cellulose is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 16.7%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying the lower clear liquid for 12h at the temperature of 80 ℃ by a vacuum drying oven to obtain the product12#Biomass based solvent with a recovery of about 99％，12#The biomass-based solvent can be recycled。
To 13#Biomass-based solventAdding inAlpha-fibresVegetarian powder5g (the polymerization degree is 1500), heating to 140 ℃, stirring for 60min until the cellulose powder is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 14.3%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the final product13#Biomass based solvent with a recovery of about 99％，13#The biomass-based solvent can be recycled。
To the direction of14#Biomass-based solventAdding inMicrocrystalline cellulose5g (the polymerization degree is 300), heating to 140 ℃, stirring for 60min until the cotton pulp cellulose is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 16.7%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying the lower clear liquid for 12h at 80 ℃ in a vacuum drying oven to obtain the product14#Biomass based solvent with a recovery of about 99％，14#The biomass-based solvent can be recycled。
To the direction of15#Biomass-based solventAdding inMicrocrystalline cellulose6g (the polymerization degree is 300), heating to 140 ℃, stirring for 60min until the microcrystalline cellulose is completely dissolved to obtain yellowish transparent solution, wherein the mass fraction of the cellulose in the solution is 23.1%, washing and filtering the obtained solution to obtain lower clear liquid, spin-drying the water by a rotary evaporator, and drying for 12h at 80 ℃ by a vacuum drying oven to obtain the microcrystalline cellulose15#Biomass based solvent with a recovery of about 99％，15#The biomass-based solvent can be recycled。
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A novel biomass-based solvent, characterized in that it comprises a polyhydroxy-containing compound and N-methylmorpholine-N-oxide;
Wherein the mass ratio of the polyhydroxy-containing compound to the N-methylmorpholine-N-oxide is 3: 1-1: 3.
2. The biomass-based solvent of claim 1, wherein the polyhydroxy-containing compound comprises at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, sorbitol, xylitol, glucose, isosorbide, isoidide, isomannide.
3. The method of any of claims 1 or 2, wherein the biomass-based solvent is prepared by dissolving a polyhydroxy-containing compound with N-methylmorpholine-N-oxide;
The mass ratio of the polyhydroxy-containing compound to the N-methylmorpholine-N-oxide is 3: 1-1: 3.
4. The method as claimed in claim 3, wherein the biomass-based solvent is obtained by weighing the polyhydroxy-containing compound and the N-methylmorpholine-N-oxide in proportion, heating to 30-100 ℃, stirring until complete mutual solubility, and cooling to room temperature.
5. A cellulosic solvent comprising at least one of the biomass-based solvent of claim 1 or 2, the biomass-based solvent produced according to the method of claim 3 or 4.
6. Use of the cellulose solvent according to claim 5 for dissolving cellulose.
7. The use according to claim 6, wherein the cellulose is added to the cellulose solvent, heated to the dissolution temperature and kept for a set time, and stirred to obtain a cellulose transparent solution.
8. The use according to claim 7, wherein the degree of polymerization of the cellulose is 300 to 1500.
9. Use according to claim 7, wherein the cellulose comprises at least one of alpha-cellulose powder, cotton pulp cellulose, cellulose filter paper or microcrystalline cellulose.
10. The use according to claim 7, wherein the dissolution temperature is 80 ℃ to 150 ℃ and the set time is 10min to 90 min;
The mass fraction of the cellulose transparent solution is 10-35.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810567535.5A CN110563972B (en) | 2018-06-05 | 2018-06-05 | Biomass-based solvent, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810567535.5A CN110563972B (en) | 2018-06-05 | 2018-06-05 | Biomass-based solvent, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110563972A true CN110563972A (en) | 2019-12-13 |
| CN110563972B CN110563972B (en) | 2021-01-26 |
Family
ID=68772033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810567535.5A Active CN110563972B (en) | 2018-06-05 | 2018-06-05 | Biomass-based solvent, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110563972B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618496A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of furandicarboxylic acid |
| CN117550587A (en) * | 2024-01-11 | 2024-02-13 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255300A (en) * | 1979-07-02 | 1981-03-10 | Akzona Incorporated | Composition and process for making precipitated cellulose-polyvinyl alcohol biconstituent composition |
| CN1468889A (en) * | 2002-06-22 | 2004-01-21 | 韩国科学技术研究院 | Process for preparing cellulose solution with excellent workability |
| CN105418943A (en) * | 2015-11-19 | 2016-03-23 | 南京林业大学 | Dissolution method of lignocellulose |
| WO2017155487A1 (en) * | 2016-03-07 | 2017-09-14 | Veritas Tekstil Konfeksiyon Pazarlama Ve Sanayi Ticaret Anonim Sirketi | Water-soluble regenerated fiber production from calluna vulgaris plant species |
-
2018
- 2018-06-05 CN CN201810567535.5A patent/CN110563972B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255300A (en) * | 1979-07-02 | 1981-03-10 | Akzona Incorporated | Composition and process for making precipitated cellulose-polyvinyl alcohol biconstituent composition |
| CN1468889A (en) * | 2002-06-22 | 2004-01-21 | 韩国科学技术研究院 | Process for preparing cellulose solution with excellent workability |
| CN105418943A (en) * | 2015-11-19 | 2016-03-23 | 南京林业大学 | Dissolution method of lignocellulose |
| WO2017155487A1 (en) * | 2016-03-07 | 2017-09-14 | Veritas Tekstil Konfeksiyon Pazarlama Ve Sanayi Ticaret Anonim Sirketi | Water-soluble regenerated fiber production from calluna vulgaris plant species |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618496A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of furandicarboxylic acid |
| CN114618496B (en) * | 2020-12-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of furandicarboxylic acid |
| CN117550587A (en) * | 2024-01-11 | 2024-02-13 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN117550587B (en) * | 2024-01-11 | 2024-03-29 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110563972B (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103524709B (en) | The preparation method of epoxy resin | |
| CN101654522A (en) | Anti-degradable solvent for dissolving cellulose and preparation method of spinning dope thereof | |
| CN102864672B (en) | Method for extracting lignin | |
| CN110563972B (en) | Biomass-based solvent, preparation method and application thereof | |
| CN105754114A (en) | Method for separating and extracting straw lignin by using eutectic ionic liquid | |
| CN107177040B (en) | A kind of cellulose solution and its dissolving method and application | |
| CN101007853A (en) | Dissolution and processing of cellulose using ionic liquids | |
| CN103408768B (en) | A kind of ionic liquid improves the method for industrial lignin quality | |
| CN102002165A (en) | Method for preparing nano lignin by using supercritical anti-solvent technology | |
| CN105418943A (en) | Dissolution method of lignocellulose | |
| CN102344495A (en) | Cyanoethyl cellulose glycerin ether and preparation method thereof | |
| CN104047067A (en) | Cellulose dissolving agent and application thereof | |
| CN102127236B (en) | Cellulose dissolvent, and application thereof in dissolving and regenerating cellulose | |
| WO2019047176A1 (en) | Method for recycling waste polyester-cotton blend fabrics | |
| CN103497158A (en) | Preparation method and application of 1-allyl,3-methylimidazole room-temperature ionic liquid | |
| CN103709264A (en) | Preparation method of carboxymethyl guar gum | |
| CN104045839A (en) | Dissolution method of cellulose subjected to anhydride microwave modification | |
| CN103290503B (en) | Cellulosic chemical modification and continuous low-temperature dissolving spinning technology and equipment | |
| CN105175342B (en) | A kind of method of ionic liquid and its homogeneous modified reed enhancing PE composite materials | |
| Wang et al. | Choline chloride-based deep eutectic solvents for degradation of waste cotton fibrics to 5-hydroxymethylfurfural | |
| CN101560258A (en) | Solvent of cellulose | |
| CN111235326A (en) | Method for catalytic hydrolysis of deep eutectic solvent-carbon-based solid acid catalyst | |
| CN106046179A (en) | Preparation method of sub-micron cellulose | |
| CN104892897A (en) | Method for preparing epoxy resin by utilizing lignin | |
| CN105399970A (en) | Method for preparing corn straw cellulose membrane by using corn straw as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |