CN115212730A - Separation membrane material based on biomass and preparation method and application thereof - Google Patents

Separation membrane material based on biomass and preparation method and application thereof Download PDF

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CN115212730A
CN115212730A CN202110415292.5A CN202110415292A CN115212730A CN 115212730 A CN115212730 A CN 115212730A CN 202110415292 A CN202110415292 A CN 202110415292A CN 115212730 A CN115212730 A CN 115212730A
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biomass
membrane material
pretreatment
separation membrane
oil
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张金明
夏钲豪
张军
米勤勇
武进
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/081—Hollow fibre membranes characterised by the fibre diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/22—Specific non-solvents or non-solvent system
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Analytical Chemistry (AREA)
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Abstract

The invention discloses a separation membrane material based on biomass, a preparation method and application thereof. When the diameter of the all-biomass micron fiber is 5-18 mu m, the membrane material formed by lapping has good separation effect on an oil-water system, and can simultaneously achieve high flux (more than 20000 L.m) 2 ·h ‑1 ) And high selectivity (100%) and is applicable to different acid-base systems andhigh salt system. Meanwhile, the separation membrane material has the advantages of simple preparation process, natural source, low price, complete biodegradation and huge application prospect in the fields of kitchen sewage, marine pollution, petrochemical industry and the like.

Description

Separation membrane material based on biomass and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials and natural polymers, and particularly relates to a membrane separation material based on biomass, and a preparation method and application thereof.
Background
The oil-water separation membrane material can simply and effectively separate oil phase and water phase, thereby having important application prospect in the fields of kitchen sewage treatment, industrial oily wastewater treatment, marine oil-gas leakage, petrochemical industry, offshore oil production and the like. However, the currently commercialized oil-water separation membrane has problems in that it is expensive, causes environmental pollution during production or use, and cannot achieve both high flux and high selectivity. Therefore, how to prepare the membrane separation material which can be completely biodegraded and has low cost becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to improve the above technical problem, the present invention provides a biomass-based separation membrane material consisting of biomass fibers having a diameter of 5 to 18 μm, illustratively 5 μm, 7 μm, 8 μm, 9.1 μm, 9.5 μm, 11 μm, 13 μm, 15 μm, 18 μm.
According to an embodiment of the present invention, the oil-water separation efficiency of the separation membrane material is not less than 90%, illustratively 90%, 94%, 95%, 96%, 97%, 98%, 99%, 100%.
According to an embodiment of the invention, the flux of the separation membrane material is > 20000 L.m 2 ·h -1 Exemplary is 21000 L.m 2 ·h -1 、22000L·m 2 ·h -1 、25000L·m 2 ·h -1 、30000L·m 2 ·h -1 、35000L·m 2 ·h -1 、40000L·m 2 ·h -1 、45000L·m 2 ·h -1 、50000L·m 2 ·h -1 、55000L·m 2 ·h -1 、58000L·m 2 ·h -1 、60000L·m 2 ·h -1 、65000L·m 2 ·h -1 、70000L·m 2 ·h -1 。
According to an embodiment of the present invention, the biomass fiber is prepared from a raw material including biomass through a spinning process. For example, the spinning method may be a dry-jet wet spinning method or an air-jet spinning method.
The spinning conditions in the preparation method of the biomass fibers are not particularly limited, and a person skilled in the art can select known conventional spinning equipment to spin under the conventional conditions.
According to embodiments of the present invention, the biomass may be selected from one, two or more of cellulose, chitosan, starch, chitin, wheat straw, corn stover, cotton stover, herb residue, setaria, pennisetum, barnyard grass, waste wood chips, bagasse, reed, corncob, fruit hulls, plant stems and leaves, and the like.
According to an embodiment of the present invention, the cellulose is selected from one, two or more of microcrystalline cellulose, cotton pulp, refined cotton, absorbent cotton, wood pulp, cotton linters, bamboo pulp, grass pulp, bacterial cellulose and the like.
According to one embodiment of the invention, the plant stems and leaves are selected from maize leaves.
According to an embodiment of the present invention, the method for preparing biomass fiber may further include a process of pretreating biomass.
According to an embodiment of the present invention, the pretreatment may be an alkali solution pretreatment, a toluene/ethanol pretreatment, a xylene/ethanol pretreatment, a petroleum ether/ethanol mixed solvent pretreatment, a boiling water pretreatment, a dilute acid pretreatment, an acetic acid/NaClO 2 At least one aqueous solution pretreatment method.
According to an embodiment of the present invention, the process of the pretreatment is selected from any one of the following five preparation methods:
the method comprises the following steps: the biomass is pretreated in an alkaline solution. For example, the lye may be aqueous NaOH.
According to one embodiment of the invention, the ratio of the amount of biomass to alkaline solution used is 1g (5-20) mL, exemplary are 1g.
According to one embodiment of the invention, the concentration of the aqueous NaOH solution is between 0.5 and 5%, exemplary 0.5%, 1%, 2%, 5%.
According to one embodiment of the invention, the temperature of the pre-treatment is 60 to 100 ℃, exemplary 60 ℃,80 ℃, 100 ℃. Further, the time of the pretreatment is 10min to 2h, and is exemplified by 10min, 30min, 1h, 1.5h, and 2h.
According to one embodiment of the invention, the method further comprises filtering, washing and drying the product pretreated by the alkali solution.
According to an exemplary embodiment of the present invention, the process of the pre-treatment is as follows: pretreating the biomass for 10 min-2 h at 60-100 ℃ by 0.5-5% NaOH aqueous solution, filtering, washing and drying.
The second method comprises the following steps: the biomass is put into at least one mixed solvent of toluene/ethanol, xylene/ethanol and petroleum ether/ethanol for reflux treatment.
According to one embodiment of the invention, the ratio of the amount of biomass to mixed solvent is 1g (20-40) mL, exemplified by 1g.
According to one embodiment of the invention, the time of the pretreatment is 8 to 14 hours, and 8 hours, 10 hours and 12 hours are exemplified. Further, the method also comprises the steps of filtering, washing and drying the product after the reflux treatment. For example, the solvent for washing may be ethanol.
According to one embodiment of the present invention, in the mixed solvent, the volume ratio of toluene/ethanol, xylene/ethanol, petroleum ether/ethanol is 1; exemplary are 1.
The third method comprises the following steps: the biomass is treated in boiling water at 100-150 ℃. For example, the treatment time is 0.5 to 2 hours, and 0.5 hour, 1 hour, and 2 hours are exemplified. Further, the method also comprises the steps of filtering, washing and drying the product after the boiling water treatment. For example, the solvent for washing may be ethanol.
The method four comprises the following steps: the biomass is treated in dilute acid. For example, the dilute acid may be dilute sulfuric acid or acetic acid.
According to one embodiment of the invention, the dilute acid concentration is 1 to 10%, exemplarily 1%, 2%, 5%, 10%.
According to one embodiment of the invention, the temperature of the pre-treatment is between 100 and 140 ℃, exemplary 100 ℃, 120 ℃, 140 ℃. Further, the time of the pretreatment is 15 to 60min, and 15min, 30min and 60min are exemplified.
According to one embodiment of the invention, the method further comprises the steps of filtering, washing and drying the product after dilute acid pretreatment.
The method five comprises the following steps: placing the biomass in acetic acid/NaClO 2 And (4) treating in an aqueous solution.
According to one embodiment of the invention, the temperature of the pre-treatment is 60 to 100 ℃, exemplary 60 ℃,80 ℃, 100 ℃. Further, the pretreatment time is 2-12h, and 2h, 5h and 10h are exemplified.
According to one embodiment of the invention, the composition further comprises p-acetic acid/NaClO 2 And filtering, washing and drying the product after the aqueous solution pretreatment.
According to one embodiment of the invention, the acetic acid/NaClO 2 In the aqueous solution, the mass concentration of acetic acid is 0.1-1.0%, illustratively 0.1%, 0.3%, 1.0%; the NaClO 2 The mass concentration of (b) is 0.5 to 3.0%, exemplarily 0.5%, 0.8%, 1.0%.
According to an embodiment of the invention, the biomass spinning solution has a concentration of 1 to 30% by mass, exemplarily 1%, 2%, 4%, 5%, 8%, 10%, 15%, 20%, 30%.
According to an embodiment of the present invention, the solvent of the biomass spinning solution may be an ionic liquid, a mixed solvent of an ionic liquid and an organic solvent, N-dimethylacetamide/lithium chloride (DMAc @)LiCl), amine oxide systems, carbamate systems, aqueous sodium hydroxide, aqueous base/urea, aqueous base/thiourea, liquid ammonia/NH 4 At least one of SCN, phosphoric acid, sulfuric acid, acetic acid, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, pyridine, chloroform, dichloromethane, ethanol, methanol, isopropanol, water, and the like.
According to an embodiment of the invention, the ionic liquid is a molten salt formed by a substituted or unsubstituted imidazole or pyridine cation and an anion and having a melting point below 100 ℃; the substituent on the imidazole or pyridine cation is C 1-6 Alkyl radical, C 1-6 At least one of alkenyl groups; the anion is at least one of halide ion, alkyl acid ion and organic phosphate ion.
According to an exemplary embodiment of the present invention, the ionic liquid is selected from at least one of 1-allyl-3-methylimidazolium chloride (AmimCl), 1-butyl-3-methylimidazolium chloride (BmimCl), ionic liquid, and 1-ethyl-3-methylimidazolium acetate (EmimAc), among others.
According to an embodiment of the present invention, the method for preparing biomass fiber further comprises a step of coagulating bath forming the fiber obtained after spinning. Preferably, the solvent for forming the coagulating bath can be one, two or three of water, alcohol and ionic liquid;
for example, the alcohol is at least one selected from the group consisting of ethanol, methanol, isopropanol, n-propanol, n-butanol, and the like.
According to an embodiment of the invention, the temperature at which the coagulation bath is shaped is between 0 and 50 ℃, preferably between 10 and 30 ℃, exemplary 0 ℃, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃.
According to exemplary embodiments of the present invention, the method of preparing the biomass fiber may be selected from any one of the following two methods of preparing:
the method comprises the following steps: dissolving biomass in a solvent, and obtaining biomass fibers in a coagulating bath by a dry-jet wet spinning method or an air flow spinning method.
The second method comprises the following steps: the biomass is pretreated, then dissolved in a solvent, and a biomass fiber is obtained in a coagulating bath by a dry-jet wet spinning method or an air flow spinning method.
The invention also provides a preparation method of the biomass-based separation membrane material, which comprises the step of preparing the separation membrane material by using biomass as a raw material through a spinning forming method, a papermaking method, a suction filtration method, a filter pressing method or a coating method.
According to an embodiment of the invention, the biomass has the meaning as described above.
According to an embodiment of the present invention, the spinning formation method may be a dry-jet wet spinning method or an air-jet spinning method, preferably an air-jet spinning method.
The spinning forming conditions in the preparation method of the separation membrane material are not particularly limited, and a person skilled in the art can select known conventional spinning equipment to spin under conventional conditions.
The invention also provides application of the biomass-based separation membrane material in a mixed system for separating oil and water. Preferably in a mixed system for separating oil and water with high flux and high selectivity.
The method is exemplarily applied to the mixed system for separating oil and water in the fields of kitchen sewage, marine pollution, petrochemical industry and the like.
According to an embodiment of the invention, the oil is an oil having a density lower than water, for example, the oil is at least one of n-hexane, cyclohexane, heptane, octane, nonane, undecane, dodecane, hexadecane, toluene, benzene, xylene, silicone oil, edible oil, peanut oil, corn oil, olive oil, and the like. Preferably at least one of n-hexane, toluene, undecane, dodecane, and edible oil, etc.
According to an embodiment of the present invention, the water may be at least one of pure water, acidic water, alkaline water, and an aqueous NaCl solution, and the like.
Preferably, the pH of the acidic water or the alkaline water is in the range of 1 to 14.
Preferably, the concentration of NaCl in the aqueous NaCl solution may range from 0 to 5mol/L, illustratively 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L.
The invention has the beneficial effects that:
the invention provides a full-bio-based separation membrane material by taking biomass as a raw material. The separation membrane material consists of micron fibers of 5-18 μm, can effectively separate oil and water, and has high flux (more than 20000 L.m) 2 ·h -1 ) And high selectivity (100%), can be applied to different acid-base systems and high-salt systems. The biomass-based separation membrane material has the advantages of simple preparation process, low cost, environmental friendliness, complete biodegradation, no toxicity, no pollution and important application prospect for industrial/marine sewage treatment.
Drawings
FIG. 1 is a scanning electron micrograph of the biomass fibers of example 6. (test apparatus: JEOL JSM-6700F.)
Fig. 2 is an optical photograph of the biomass membrane material in example 6.
FIG. 3 shows the separation efficiency of the biomass membrane material in example 6 for n-hexane/water, dodecane/water, toluene/water, and soybean oil/water. (test instrument: infrared OIL tester OIL 480.)
Fig. 4 is the flux of biomass membrane material in example 6 for n-hexane/water, dodecane/water, toluene/water, soybean oil/water. (test apparatus: infrared OIL tester OIL 480.)
FIG. 5 shows the separation efficiency of the biomass membrane material in example 7 on n-hexane/water (pH of aqueous phase 1, 3, 5, 7, 9, 11, 13; test apparatus: infrared OIL tester OIL 480.)
FIG. 6 is the flux of the biomass membrane material in example 7 for n-hexane/water. ( Wherein the pH of the water phase is 1, 3, 5, 7, 9, 11 and 13 respectively. The test instrument is as follows: infrared OIL level gauge OIL480. )
FIG. 7 shows the separation efficiency of the biomass membrane material from an aqueous solution of n-hexane/NaCl in example 8. ( The NaCl concentrations in the NaCl aqueous solution were 0.5M, 1M, 2M, 3M, and 4M, respectively. The test instrument is as follows: infrared OIL level gauge OIL480. )
FIG. 8 shows the results of the flux performance test of the biomass membrane material in example 8 on n-hexane/NaCl aqueous solution. ( The NaCl concentrations in the NaCl aqueous solution were 0.5M, 1M, 2M, 3M, and 4M, respectively. The test instrument is as follows: infrared OIL level gauge OIL480. )
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Microcrystalline cellulose is selected as a raw material. 92g of 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid are weighed, 8g of dried microcrystalline cellulose is added and dissolved by stirring at 80 ℃ for 60 minutes to form a uniform transparent solution (the solid content of the microcrystalline cellulose/AmimCl solution is 8%). Cellulose micron fiber is obtained by an air flow spinning method with water at 20 ℃ as a coagulating bath. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 10 mu m.
Respectively mixing n-hexane, toluene and edible oil with water according to a volume ratio of 1 2 ·h -1 、36852L·m 2 ·h -1 、22563L·m 2 ·h -1 。
Example 2
The cotton pulp is selected as the raw material. 5g of cotton pulp and 95g of AmimCl ionic liquid are stirred and dissolved for 1 hour at 90 ℃ to form a uniform solution (the solid content of the cotton pulp/AmimCl solution is 5%). Centrifuging, and performing dry-jet wet spinning with water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 7 mu m.
The normal hexane, the toluene and the edible oil are respectively mixed with water according to the volume ratio of 1Are respectively 35265L m 2 ·h -1 、30205L·m 2 ·h -1 、22152L·m 2 ·h -1 。
Example 3
Corn starch is selected as a raw material. 8g of corn starch and 92g of AmimCl ionic liquid are taken and stirred at 90 ℃ to be dissolved for 3 hours to form a uniform solution (the solid content of the corn starch/AmimCl solution is 8%). Centrifuging, airflow spinning, and taking water at 20 ℃ as a coagulating bath to obtain the micron fibers. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 18 mu m.
The n-hexane, the toluene and the edible oil are respectively mixed with water according to the volume ratio of 1 2 ·h -1 。
Example 4
Selecting pennisetum alopecuroides powder as a raw material. 8g of pennisetum alopecuroides powder of 500 meshes and 92g of 1-butyl-3-methylimidazolium chloride (BmimCl) ionic liquid are stirred and dissolved for 3 hours at 100 ℃ to form a uniform solution (the solid content of the pennisetum alopecuroides powder/BmimCl solution is 8%). Centrifuging, airflow spinning, and taking water at 20 ℃ as a coagulating bath to obtain the micron fibers. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 13 mu m.
Respectively mixing n-hexane, toluene and edible oil with water according to a volume ratio of 1 2 ·h -1 、46321L·m 2 ·h -1 、35259L·m 2 ·h -1 。
Example 5
Selecting pennisetum alopecuroides powder as a raw material. 8g of pennisetum alopecuroides powder of 600 meshes and 92g of AmimCl are stirred and dissolved for 3 hours at 90 ℃ to form a uniform solution (the solid content of the pennisetum alopecuroides powder/AmimCl solution is 8%). Centrifuging, and performing dry-jet wet spinning by taking water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 18 mu m.
Mixing n-hexane, toluene andthe edible oil is respectively mixed with water according to the volume ratio of 1 2 ·h -1 、50214L·m 2 ·h -1 、40252L·m 2 ·h -1 。
Example 6
Selecting pennisetum alopecuroides powder as a raw material. Adding 10g of 500 mesh pennisetum powder into 100mL of 1% NaOH aqueous solution, treating at 60 deg.C for 1h, filtering, washing with ethanol, and drying. 4g of the treated grass meal and 96g of AmimCl are stirred and dissolved for 3 hours at 90 ℃ to form a uniform solution, and the solid content of the grass meal/AmimCl solution is 4%. Centrifuging, air spinning, and taking water at 20 ℃ as a coagulating bath to obtain the micron fibers. Then the membrane material is prepared by washing, filter pressing and drying at 60 ℃ (figure 2).
Fig. 1 is a scanning electron micrograph of the biomass fibers in this example, from which it can be seen that: the diameter of the fiber in the biological membrane material is 10 μm.
N-hexane, dodecane, toluene and edible oil are respectively mixed with water according to the volume ratio of 1 2 ·h -1 、42156L·m 2 ·h -1 、39174L·m 2 ·h -1 、25515L·m 2 ·h -1 (as shown in fig. 4).
Example 7
Wheat straw is selected as a raw material. Pulverizing wheat straw, drying, weighing 10g of wheat straw powder, adding 1mL of acetic acid/3 g of NaClO 2 300mL of water, treated at 80 ℃ for 2h, filtered, washed with water and dried. Then 4g of the pretreated wheat straw powder and 96g of AmimCl ionic liquid are stirred and dissolved for 3h at 90 ℃ to form a uniform solution (the solid content of the wheat straw/AmimCl solution is 4%). Centrifuging, and carrying out air flow spinning with water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, papermaking and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 11 mu m.
Mixing n-hexane and water according to the volume ratio of 1,performing oil-water separation experiment, wherein the water phase has different pH values, the oil-water separation efficiency is 100% (as shown in FIG. 5), and the flux is 44056 L.m respectively when the pH of the water phase is 1, 3, 5, 7, 9, 11, 13 2 ·h -1 、39787L·m 2 ·h -1 、37956L·m 2 ·h -1 、44066L·m 2 ·h -1 、34838L·m 2 ·h -1 、39507L·m 2 ·h -1 、27004L·m 2 ·h -1 (as shown in fig. 6).
Example 8
Selecting pennisetum alopecuroides powder as a raw material. 10g of pennisetum alopecuroides powder of 500 meshes is added into 100mL of 1-percent NaOH solution to be treated for 1 hour at 60 ℃, filtered, washed by water for 1 time, washed by ethanol for 2 times and dried. 4g of the pretreated pennisetum alopecuroides powder and 96g of 1-ethyl-3-methylimidazolium acetate (EmimAc) ionic liquid are stirred and dissolved for 1 hour at 90 ℃ to form a uniform solution (the solid content of the pennisetum alopecuroides powder/EmimAc solution is 4%). Centrifuging, and carrying out air flow spinning with water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, papermaking and drying at 60 ℃ are carried out to prepare the membrane material, wherein the fiber diameter is 9.5 mu m.
The normal hexane, the toluene and the edible oil are respectively mixed with water according to the volume ratio of 1 2 ·h -1 、49565L·m 2 ·h -1 、38562L·m 2 ·h -1 。
The n-hexane and the NaCl aqueous solution were mixed at a volume ratio of 1:1, and the total mass of the mixed solution was 200g, and oil-water separation experiments were performed, and the oil-water separation efficiency was 100% (as shown in fig. 7), and when the NaCl concentration in the NaCl aqueous solution was 0.5M, 1M, 2M, 3M, and 4M, the flux was 44466L · M, respectively, when the NaCl concentration was 0.5M, 1M, 2M, 3M, and 4M, respectively 2 ·h -1 、37500L·m 2 ·h -1 、32281L·m 2 ·h -1 、27439L·m 2 ·h -1 、25570L·m 2 ·h -1 (as shown in fig. 8).
Example 9
Corn leaves are selected as raw materials. 10g of the pulverized corn leaf powder was treated with 100mL of 1% NaOH aqueous solution at 60 ℃ for 1 hour, filtered, washed with water 1 time, washed with ethanol 2 times, and dried. 4g of the pretreated corn leaf powder and 96g of Emimac ionic liquid are stirred and dissolved for 1 hour at 90 ℃ to form a uniform solution (the solid content of the corn leaf/Emimac solution is 4%). Centrifuging, air-flow spinning with 20 deg.C water as coagulating bath, collecting fiber on collecting roller, and drying at 60 deg.C to obtain membrane material with fiber diameter of 11 μm.
Respectively mixing n-hexane, undecane and edible oil with water according to a volume ratio of 1 2 ·h -1 、54521L·m 2 ·h -1 、46895L·m 2 ·h -1 。
Example 10
Corn stalks are selected as raw materials. 10g of the pulverized corn stalk powder was added to 100mL of 2% NaOH aqueous solution and treated at 60 ℃ for 1 hour, filtered, washed with water for 1 time, washed with ethanol for 2 times, and dried. 6g of the pretreated corn stalk powder and 94g of AmimCl ionic liquid are stirred and dissolved for 2 hours at 90 ℃ to form a uniform solution, and the solid content of the corn stalk/AmimCl solution is 6%. Centrifuging, and performing dry-jet wet spinning by using water at the temperature of 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, papermaking and drying at 60 ℃ are carried out to prepare the membrane material, wherein the fiber diameter is 8 mu m.
Respectively mixing n-hexane, undecane and edible oil with water according to a volume ratio of 1 2 ·h -1 、44125L·m 2 ·h -1 、29854L·m 2 ·h -1 。
Example 11
Bagasse is selected as a raw material. 10g of the pulverized bagasse was taken and added to 300mL of toluene: ethanol =2, 1 (v/v), at 150 ℃ for 12h, filtered, washed with ethanol, and dried. 5g of pretreated bagasse and 95g of AmimCl were dissolved at 90 ℃ with stirring for 3h to form a homogeneous solution. Centrifuging, and performing dry-jet wet spinning by using water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, papermaking and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 16 mu m.
Respectively mixing normal hexane, undecane and edible oil with water according to a volume ratio of 1 2 ·h -1 、44115L·m 2 ·h -1 、30523L·m 2 ·h -1 。
Example 12
Bulrush is selected as a raw material. 10g of the crushed reed leaf powder was added to 100mL of 2% NaOH solution and treated at 60 ℃ for 0.5h, filtered, washed with ethanol, and dried. 4g of the pretreated reed leaf powder and 96g of AmimCl/DMSO (8. Centrifuging, and carrying out air flow spinning with water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, filter pressing and drying at 60 ℃ are carried out to prepare the membrane material, wherein the fiber diameter is 13 mu m.
Respectively mixing n-hexane, undecane and edible oil with water according to a volume ratio of 1 2 ·h -1 、60241L·m 2 ·h -1 、35262L·m 2 ·h -1 。
Example 13
Corncobs are selected as raw materials. 5g of dried corncob powder and 95g of AmimCl ionic liquid are stirred and dissolved for 1 hour at 90 ℃ to form a uniform solution, and the solid content of the corncob/AmimCl solution is 5%. Centrifuging, performing air flow spinning, taking water at 20 ℃ as a coagulating bath, and collecting on a collecting roller to obtain the micron fibers. Then dried at 60 ℃ to prepare a membrane material in which the fiber diameter is 11 μm.
The normal hexane, the undecane and the edible oil are respectively mixed with water according to a volume ratio of 1 2 ·h -1 、53565L·m 2 ·h -1 、42371L·m 2 ·h -1 。
Example 14
Chitosan is selected as a raw material. 6g of dried chitosan and 94g of 5wt% aqueous acetic acid solution were weighed, dissolved by stirring at room temperature, and after 60 minutes, a uniform transparent solution was formed (the solid content of the chitosan/aqueous acetic acid solution was 6%). Obtaining chitosan micron fiber by an airflow spinning method with 20 ℃ ethanol as a coagulating bath, washing, filtering, drying at 60 ℃ and preparing a membrane material, wherein the diameter of the fiber is 9.1 mu m.
Respectively mixing n-hexane, toluene and edible oil with water according to a volume ratio of 1 2 ·h -1 、35794L·m 2 ·h -1 、27043L·m 2 ·h -1 。
Example 15
The cotton pulp is selected as the raw material. 5g of cotton pulp and 95g of AmimCl ionic liquid are stirred and dissolved for 1 hour at 90 ℃ to form a uniform solution (the solid content of the cotton pulp/AmimCl solution is 5%). Centrifuging, and performing dry-jet wet spinning by taking water at 20 ℃ as a coagulating bath to obtain the micron fiber. Then washing, filtering and drying at 60 ℃ to prepare the membrane material, wherein the fiber diameter is 22 mu m.
Respectively mixing n-hexane, toluene and edible oil with water according to a volume ratio of 1 2 ·h -1 、52091L·m 2 ·h -1 、43510L·m 2 ·h -1 。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A biomass-based separation membrane material is characterized in that the separation membrane material is composed of biomass fibers with the diameter of 5-18 mu m.
Preferably, the oil-water separation efficiency of the separation membrane material is not lower than 90%.
Preferably, the flux of the separation membrane material is more than 20000 L.m 2 ·h -1 。
2. The separation membrane material of claim 1, wherein the biomass fibers are prepared from a feedstock comprising biomass by a spinning process.
Preferably, the spinning method may be a dry-jet wet spinning method or an air-jet spinning method.
3. The separation membrane material of claim 1 or 2, wherein the biomass may be one, two or more selected from cellulose, cotton pulp, chitosan, starch, chitin, wheat straw, corn straw, cotton straw, herb residue, setaria viridis, pennisetum, barnyard grass, waste wood chips, bagasse, reed, corncob, fruit hull, plant stems and leaves, and the like.
Preferably, the cellulose is selected from one, two or more of microcrystalline cellulose, refined cotton, absorbent cotton, wood pulp, cotton linters, bamboo pulp, grass pulp, bacterial cellulose and the like.
Preferably, the plant stems and leaves are selected from maize leaves.
4. The separation membrane material of claim 2, wherein the preparation method of the biomass fiber further comprises a process of pretreating the biomass.
Preferably, the pretreatment may be an alkali solution pretreatment, a toluene/ethanol, xylene/ethanol, petroleum ether/ethanol mixed solvent pretreatment, a boiling water pretreatment, a dilute acid pretreatment, acetic acid/NaClO 2 At least one aqueous solution pretreatment method.
5. The separation membrane material of claim 4, wherein the pretreatment process is selected from any one of the following five preparation methods:
the method comprises the following steps: pretreating the biomass in an alkaline solution. For example, the lye may be an aqueous NaOH solution.
Preferably, the dosage ratio of the biomass to the alkali solution is 1g (5-20) mL.
Preferably, the concentration of the NaOH aqueous solution is 0.5-5%.
Preferably, the temperature of the pretreatment is 60-100 ℃, and the time of the pretreatment is 10 min-2 h.
The second method comprises the following steps: the biomass is put into at least one mixed solvent of toluene/ethanol, xylene/ethanol and petroleum ether/ethanol for reflux treatment.
Preferably, the dosage ratio of the biomass to the mixed solvent is 1g (20-40) mL.
Preferably, the time of the pretreatment is 8-14 h, and the volume ratio of toluene/ethanol, xylene/ethanol and petroleum ether/ethanol in the mixed solvent is 1.
The third method comprises the following steps: the biomass is treated in boiling water at 100-150 ℃. For example, the treatment time is 0.5 to 2 hours.
The method four comprises the following steps: the biomass is treated in dilute acid. For example, the dilute acid may be dilute sulfuric acid or acetic acid.
Preferably, the concentration of the dilute acid is 1 to 10 percent.
Preferably, the temperature of the pretreatment is 100-140 ℃, and the time of the pretreatment is 15-60 min.
The method five comprises the following steps: placing the biomass in acetic acid/NaClO 2 And (4) treating in an aqueous solution.
Preferably, the temperature of the pretreatment is 60-100 ℃, and the time of the pretreatment is 2-12h.
Preferably, the acetic acid/NaClO 2 In the aqueous solution, the mass concentration of the acetic acid is 0.1-1.0%; the NaClO 2 The mass concentration of (A) is 0.5-3.0%.
6. The separation membrane material of any one of claims 1-5, wherein the biomass spinning solution is at a concentration of 1-30% by mass.
Preferably, the solvent of the biomass spinning solution can be formed by ionic liquid, ionic liquid and organic solventMixed solvent, N-dimethylacetamide/lithium chloride (DMAc/LiCl), amine oxide systems, carbamate systems, aqueous sodium hydroxide solutions, aqueous base/urea solutions, aqueous base/thiourea solutions, liquid ammonia/NH 4 At least one of SCN, phosphoric acid, sulfuric acid, acetic acid, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, pyridine, chloroform, dichloromethane, ethanol, methanol, isopropanol, water, and the like.
Preferably, the ionic liquid is at least one selected from 1-allyl-3-methylimidazole chloride salt (AmimCl), 1-butyl-3-methylimidazole chloride salt (BmimCl), 1-ethyl-3-methylimidazole acetate (EmimAc), and the like.
7. The separation membrane material of any one of claims 1 to 6, wherein the preparation method of the biomass fiber can be selected from any one of the following two preparation methods:
the method comprises the following steps: dissolving biomass in a solvent, and obtaining biomass fibers in a coagulating bath by a dry-jet wet spinning method or an air flow spinning method.
The second method comprises the following steps: the biomass is pretreated, then dissolved in a solvent, and a biomass fiber is obtained in a coagulating bath by a dry-jet wet spinning method or an air flow spinning method.
8. The method for producing the separation membrane material according to any one of claims 1 to 7, wherein the production method comprises producing the separation membrane material from a biomass as a raw material by a spinning method, a papermaking method, a suction filtration method, a filter pressing method, or a coating method.
Preferably, the biomass has the meaning as defined in claim 2.
Preferably, the spinning formation method may be a dry-jet wet spinning method or an air-jet spinning method, preferably an air-jet spinning method.
9. Use of the separation membrane material of any one of claims 1 to 7 for separating a mixed system of oil and water. Preferably, in a mixed system for separating oil and water with high flux and high selectivity.
The method is exemplarily applied to the mixed system for separating oil and water in the fields of kitchen sewage, marine pollution, petrochemical industry and the like.
10. The use of claim 9, wherein the oil is at least one of n-hexane, cyclohexane, heptane, octane, nonane, undecane, dodecane, hexadecane, toluene, benzene, xylene, silicone oil, edible oil, peanut oil, corn oil, olive oil, and the like.
CN202110415292.5A 2021-04-18 2021-04-18 Separation membrane material based on biomass and preparation method and application thereof Pending CN115212730A (en)

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