CN109569322A - A kind of super hydrophilic and underwater superoleophobic cellulose membrane and preparation method thereof - Google Patents
A kind of super hydrophilic and underwater superoleophobic cellulose membrane and preparation method thereof Download PDFInfo
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- CN109569322A CN109569322A CN201811460439.7A CN201811460439A CN109569322A CN 109569322 A CN109569322 A CN 109569322A CN 201811460439 A CN201811460439 A CN 201811460439A CN 109569322 A CN109569322 A CN 109569322A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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- 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
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a kind of super hydrophilic and underwater superoleophobic cellulose membranes and preparation method thereof, belong to the oily water separation technique field in petroleum industry；The present invention uses chemical fibre spinning method, and hydrophilic cellulose nanofiber is spun into cellulose fibre, and it is the super hydrophilic and underwater superoleophobic cellulose membrane of 50~500 purposes that cellulose fibre, which is woven into mesh number, by mechanical weaving method later；Contact angle ≈ 0 of the water on cellulose membrane surfaceo, contact angle ≈ 150 of the underwater oil droplet on cellulose membrane surfaceo；The separation nethike embrane has many advantages, such as that hole Penetration ration is high, water-oil separating imitates that (> 99%), separating property are stable, degradable, and preparation process is simple, raw material sources are rich and easy to get, low in cost and environmental-friendly；The oil-water separation mesh film of the method for the present invention preparation, can be used for handling the oily waste water being discharged in oil exploitation, pipe leakage, marine transportation, textile industry, food processing industry, machinery industry or chemical industry.
Description
Technical field
Present invention relates particularly to a kind of super hydrophilic and underwater superoleophobic cellulose membranes and preparation method thereof, belong to petroleum work
Oily water separation technique field in industry.
Background technique
A large amount of oily waste waters all can in oil exploitation, transport and purification process and caused by other mankind's activities
Harmful and irreversible influence is generated on mankind itself's health and natural environment；Meanwhile it is increasingly depleted with fossil resource,
The recycling of oil is also increasingly subject to the attention of people in waste water；Therefore, there is an urgent need to develop suitable device and method with
Just it realizes to simple and effective the recycling of oil in waste liquid, in this way while reduction oily waste water endangers, and may be implemented
The efficient utilization of fossil resource；In numerous oily water separation techniques, by the features such as low energy consumption and separative efficiency is high, UF membrane skill
Art is increasingly subject to the concern of people.
Firstly, disclosing one kind application No. is the Chinese patent application of 201710565096.X has super-hydrophobic and super oleophylic
Water-oil separating cork filter membrane, the preparation of the filter membrane and realize that filter membrane surface has modification (the passing through of special wellability
Modifying process is learned to realize) it is excessively complicated, limit the large-scale industrial application of this kind of filter membrane material；
Secondly, application No. is 201610540934.3 Chinese patent applications to disclose the high oil rub resistance using fluorine resin as substrate
Water-oil separationg film, azodiisobutyronitrile etc. has been used in the synthesis primary raw material of the seperation film has the shortcomings that inflammable and toxicity is big
Organic matter so that the preparation process risk of this kind of filter membrane is high and pollutes the environment；
Its waste of above two filter membrane, which all exists, to be difficult to realize degrade, and secondary pollution can be caused to ask environment after use
Topic；
Application No. is 201610303648.5 Chinese patent applications to disclose a kind of natural super hydrophilic filter membrane, although the filtering
It is not related to complex and costly high chemical modification process in the preparation process of film, but needs to lead to cellulose during the preparation process
The mode of filtering or coating places it between two-layer fabrics net, and this two-layer fabrics net is in chemical property and physical property
It differs greatly with cellulose, it is difficult to ensure that the cellulose to play a leading role in oil water separation process will not be shelled from fabric web
It falls, to be difficult to ensure the stable greasy dirt separating capacity of filter membrane；
Therefore it provides a kind of raw material is easy to get, preparation is simple, and performance is stablized, and oil-water separation is good, can be recycled, waste
Degradable environmentally protective cellulose membrane is research purpose of the invention.
Summary of the invention
The purpose of the present invention is to provide a kind of super hydrophilic and underwater superoleophobic cellulose membranes and preparation method thereof, are used for
The water-oil separating processing of oily waste water in human being's production and life；It is fine improving filter membrane using the natural hydrophilicity of cellulose
Under the premise of dimension table surface roughness, so that target filter membrane has super hydrophilic and underwater superoleophobic characteristic；In addition, passing through machinery
Braid mean obtains keeping its separating property stable and useless only containing cellulose fibre and without the cellulose membrane that other fabric webs are formed
Gurry may be implemented to degrade.
The technical solution adopted by the invention is as follows: a kind of super hydrophilic and underwater superoleophobic cellulose membrane, it is characterised in that:
Be made by warp thread and weft yarn by mechanical weaving method, warp thread and weft yarn are interweaved, through thermo-compression bonding formed mesh number be 50~
The cellulose membrane of 500 mesh；The warp thread and weft yarn use diameter for 10~1000 microns of cellulose fibre；The cellulose
Fiber is made by cellulose nano-fibrous by chemical fibre spinning method；Between interval and weft yarn between the warp thread
Interval is 25 ~ 3962 microns.
A kind of preparation method of super hydrophilic and underwater superoleophobic cellulose membrane, which comprises the following steps:
(1) prepare cellulose nano-fibrous dispersion liquid: prepare solid masses percentage be 0.1~1%, fibre diameter be 1~
300 nanometers of cellulose nano-fibrous dispersion liquid or solid masses percentage is 0.1~1%, fibre diameter is 1~300 to receive
Rice and cellulose nano-fibrous dispersion liquid of the granularity less than 1 centimetre；
(2) to above-mentioned steps (1) preparation cellulose nano-fibrous dispersion liquid use chemical fibre spinning method obtain diameter for
10~1000 microns of cellulose fibre, the chemical fibre spinning method are dry spinning or wet spinning；
The process for wherein preparing cellulose fibre using dry spinning technology is as follows:
Liquor natrii hypochloritis, volume ratio is added in the cellulose nano-fibrous dispersion liquid that (2-1) is prepared to step (1) are as follows: fiber
Plain nanofiber dispersion liquid: liquor natrii hypochloritis=100:1 ~ 5 stirs evenly, and glacial acetic acid is added dropwise after reaction 30 minutes to neutrality,
25 ~ 35 degrees Celsius lower heating stirring 30 ~ 90 minutes, concentration formed viscosity be 5000 ~ 10000 pascal seconds spinning solution, will
After de-soak is filtered by vacuum in spinning solution, temperature be 25 degrees Celsius, relative humidity 45%, winding distance under the conditions of 8-12 centimetres,
It squeezes out to obtain as-spun fibre cellulose fiber using dry spinning device；
The as-spun fibre cellulose fiber that (2-2) prepares step (2-1) through wind speed is 0.3 ~ 0.5 metre per second (m/s), temperature is 40 ~ 60 Celsius
Drawing is blown under the hot wind of degree 10 ~ 15 minutes, the twist is/10 centimetres of twisting of 400 ~ 600 twirl, is that 100 ~ 120 degrees Celsius of heat are fixed in temperature
Type 5 ~ 10 minutes, then go to twist and obtain the cellulose fibre that diameter is 10~1000 microns；
The process for wherein preparing cellulose fibre using wet spinning technology is as follows:
For the cellulose nano-fibrous dispersion liquid that (2-3) prepares step (1) through filtering, deaeration, formation temperature is 15 ~ 120 Celsius
Spend spinning solution；
The spinning solution that (2-4) prepares step (2-3) after metering pump, filter from spinneret orifice spray, into temperature be 20 ~
In 90 degrees Celsius of coagulating baths, coagulating bath be dimethyl acetamide, dimethylformamide, dimethyl sulfoxide aqueous solution in it is any
One kind, and solidifying bath concentration is 25 ~ 70%, obtains as-spun fibre cellulose fiber；
The as-spun fibre cellulose fiber that (2-5) prepares step (2-4) by total stretch ratio be 0.5 ~ 7.0 drawing-off, washing, on
Oil, baking process obtain the cellulose fibre that diameter is 10~1000 microns；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 50~500 mesh, and the interval between interval and weft yarn between the warp thread is equal
It is 25 ~ 3962 microns.
Preferably, the preparation method, which is characterized in that step (1) prepares cellulose nano-fibrous dispersion liquid, wherein
The first preparation process it is as follows:
(1-1) mixes sodium hydroxide and urea, mixed mass percent are as follows: sodium hydroxide: urea=1:(0.5~2),
Deionized water is added in mixture, is uniformly mixing to obtain the first solution, wherein sodium hydroxide account for total solution mass percent 4~
8%；
Commercial plant cellulose is added in above-mentioned first solution by (1-2) under conditions of mechanical stirring, the quality hundred of addition
Divide ratio are as follows: plant cellulose powder: the first solution=1:(25~100), obtain mixed solution；By the mixed solution temperature be 0
It places 3~8 hours, takes out under~-20 degrees celsius, it is molten to obtain second after stirring 15~30 minutes under normal temperature and pressure conditions
Liquid；Ethyl alcohol or methanol are added in the second solution, the volume ratio of addition are as follows: ethyl alcohol or methanol: the second solution=1:(0.7~
1.4) after, standing 0.4~0.7 hour, 2~5 solvent replacements is carried out with isometric deionized water of the second solution, obtain solid
The cellulose nano-fibrous dispersion liquid that mass percent is 0.1~1%, fibre diameter is 1~300 nanometer.
Preferably, the preparation method, which is characterized in that step (1) prepares cellulose nano-fibrous dispersion liquid, and second
Kind preparation process is as follows:
(1-3) prepares acetobacter xylinum fermentation culture: the mass percent of acetobacter xylinum fermentation culture are as follows: glucose 2%, egg
White peptone 0.5%, yeast powder 0.5%, five water disodium hydrogen phosphates 0.27%, mass concentration are no more than citric acid-hydrate of 3 grams per liters
0.115%, pH value is to sterilize 20 minutes under 4~6,121 degrees Celsius, is sufficiently vibrated；By the seed training of commercial acetobacter xylinum strain
Nutrient solution is inoculated into above-mentioned acetobacter xylinum fermentation culture, and the seed culture fluid of acetobacter xylinum strain is acetobacter xylinum fermented and cultured
It is cultivated 15 days under 30 degrees Celsius sufficiently after oscillation, obtains cellulose aquagel in the 8~25% of liquid quality；By cellulose water-setting
Glue is placed in the NaOH aqueous solution that molar concentration is 5%, is heated to 90 degrees Celsius, keeps the temperature 10 hours, then be placed in deionized water,
15 hours are kept the temperature under 85 degrees Celsius, obtains cellulose aquagel block；
Above-mentioned cellulose aquagel block is put into sulfuric acid, hydrochloric acid, nitric acid, the hydrogen that molar concentration is 3~10 mol/Ls by (1-4)
In any one in bromic acid, hydroiodic acid, it is dispersed with stirring under 60~90 degrees Celsius 0.3~2 hour, is washed with deionized water,
Make solution to neutrality, obtains that solid masses percentage is 0.1~1%, fibre diameter is 1~300 nanometer cellulose nano-fibrous
Dispersion liquid；
Or: above-mentioned cellulose aquagel block is put into mechanical crusher, after deionized water is added, Mechanical Crushing at normal temperature
After 3~8 minutes, obtain that solid masses percentage is 0.1~1%, fibre diameter is 1~300 nanometer and granularity is less than 1 centimetre
Cellulose nano-fibrous dispersion liquid.
The beneficial effects of the present invention are: firstly, the parent that the cellulose membrane of the method for the present invention preparation is natural using cellulose
The rough surface of aqueous energy binding fiber, so that goal filtering seperation film shows super hydrophilic and underwater superoleophobic characteristic；It saves
Surface chemical modification step complicated, with high costs and pollution indispensable in other special wellability seperation film preparation process is gone
Suddenly；The preparation process of water-oil separationg film is greatly simplified, while reducing the preparation cost of membrane material；Secondly, cellulose membrane
Super hydrophilic and underwater superoleophobic characteristic makes the seperation film be difficult to be polluted and blocked by greasy dirt during the separation process, Jin Erwei
It the stable separating property of seperation film and recycles and provides possibility；Third, this method preparation cellulose membrane in without change
It learns property and physical property differs biggish other fabric webs, avoid the possibility that separation decorative layer is removed from other fabric webs
Property, preparation process is simple, and the separation film properties prepared are stablized；4th, the substrate fiber element abundance that the present invention selects is easy
, therefore cellulose membrane can be produced in enormous quantities with cheap cost；In addition, super hydrophilic and underwater superoleophobic fibre of the invention
Plain film is tieed up without harmful substance and may be implemented to degrade, therefore is green and environmental-friendly.The fiber of the method for the present invention preparation
Plain film can be used for handling from oil exploitation, pipe leakage, marine transportation, textile industry, food processing industry, machinery industry or chemical industry
The oily waste water being discharged in industry；
The present invention uses chemical fibre spinning method, and hydrophilic cellulose nanofiber is spun into cellulose fibre, Zhi Houtong
Crossing mechanical weaving method and cellulose fibre is woven into mesh number is the super hydrophilic and underwater superoleophobic cellulose of 50~500 purposes
Film；Contact angle ≈ 0 of the water on cellulose membrane surfaceo, contact angle ≈ 150 of the underwater oil droplet on cellulose membrane surfaceo；The separate mesh
Film has many advantages, such as that hole Penetration ration height, water-oil separating imitate (> 99%), separating property stabilization, degradable, preparation process letter
List, raw material sources are rich and easy to get, low in cost and environmental-friendly；The oil-water separation mesh film of the method for the present invention preparation, can be used for locating
Manage the oil-containing being discharged in oil exploitation, pipe leakage, marine transportation, textile industry, food processing industry, machinery industry or chemical industry
Waste water.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range；Experimental method used in embodiment is conventional method unless otherwise specified；Material, reagent used etc., such as nothing
Specified otherwise is commercially available.
Embodiment 1
(1) it is separately added into 3.8 grams of sodium hydroxides, 5.5 grams of urea and 40.8 ml deionized waters in 250 milliliters of beakers, stirs
Uniformly obtain the first solution；
1 gram of commercial plant cellulose is added in above-mentioned first solution under conditions of mechanical stirring later, obtains mixing molten
Mixed solution is placed in refrigerator by liquid, and constant temperature is placed 5 hours under subzero 12.3 degrees celsius；It takes out, in 25 degrees Celsius of items
It is stirred 20 minutes under part and obtains transparency cellulose lye；Solvent is carried out to the transparency cellulose lye using isometric dehydrated alcohol
After standing 30 minutes, the nanofibers of cellulose are precipitated, then washed 3 times with isometric deionization in displacement in alcoholic solution,
And the amount of deionized water for controlling addition obtains the dispersion liquid for the nanofiber that mass fraction of solids is 1%；
(2) liquor natrii hypochloritis, volume ratio is added in the cellulose nano-fibrous dispersion liquid prepared to step (1) are as follows: cellulose
Nanofiber dispersion liquid: liquor natrii hypochloritis=100:1 stirs evenly, and glacial acetic acid is added dropwise after reaction 30 minutes to neutrality, 25
Degrees Celsius lower heating stirring 40 minutes, concentration formed the spinning solution that viscosity is 5000 pascal seconds, and spinning solution vacuum filtration is gone
After bubble, temperature be 25 degrees Celsius, relative humidity 45%, winding distance is squeezes under the conditions of 8 centimetres using dry spinning device
As-spun fibre cellulose fiber is obtained out；By obtained as-spun fibre cellulose fiber through wind speed be 0.3 metre per second (m/s), temperature is 40 degrees Celsius
Blow drawing 10 minutes under hot wind, the twist is 400 to twist/10 centimetres of twisting, temperature be 100 degrees Celsius thermal finalization 5 minutes, then go to twist
The cellulose fibre for being 110 microns to diameter；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 100 mesh, and the interval between interval and weft yarn between the warp thread is 150
Micron；
(4) cellulose membrane obtained above is placed in air, measures the contact angle ≈ 0 of nanofiber film surface at this time and watero,
The contact angle ≈ 150 of underwater cellulose membrane and diesel oilo；Cellulose membrane is fixed among simple glass flange later, upper and lower side
Respectively feed glass pipe and discharging glass tube, by diesel oil (contaminate diesel oil for red liquid using 0.5 gram of three dyestuff of the Sudan) and
(volume ratio of diesel oil and water is 2:3 to 100 milliliters of the mixture of water, obtains the oil droplet of diesel oil in water after magnetic agitation 25 minutes
Partial size is 30 microns) it is poured in above-mentioned oil-water separation mesh film by top feed glass pipe, water passes through oil-water separation mesh film under
Side's discharging glass tube outflow, while diesel oil is blocked in the upper end of oil-water separation mesh film, can realize oil mixing with water in 1.6 minutes
The purpose of object separation, and separation rate is 99.1%.
Embodiment 2
(1) it is separately added into 3.8 grams of sodium hydroxides, 5.5 grams of urea and 40.8 ml deionized waters in 250 milliliters of beakers, stirs
Uniformly obtain the first solution；
1 gram of commercial plant cellulose is added in above-mentioned first solution under conditions of mechanical stirring later, obtains mixing molten
Mixed solution is placed in refrigerator by liquid, and constant temperature is placed 5 hours under subzero 12.3 degrees celsius；It takes out, in 25 degrees Celsius of items
It is stirred 20 minutes under part and obtains transparency cellulose lye；Solvent is carried out to the transparency cellulose lye using isometric dehydrated alcohol
After standing 30 minutes, the nanofibers of cellulose are precipitated, then washed 3 times with isometric deionization in displacement in alcoholic solution,
And the amount of deionized water for controlling addition obtains the dispersion liquid for the nanofiber that mass fraction of solids is 1%；
(2) by the cellulose nano-fibrous dispersion liquid of step (1) preparation through filtering, deaeration, formation temperature is 20 degrees Celsius of spinning
Stoste；The spinning solution of preparation is sprayed after metering pump, filter from spinneret orifice, is that 30 degrees Celsius of coagulating baths are into temperature
In the aqueous solution of dimethyl acetamide, and the concentration of coagulating bath dimethyl acetamide is 30%, obtains as-spun fibre cellulose fiber；It will
As-spun fibre cellulose fiber by total stretch ratio be 2.0 drawing-off, wash, oil, baking process obtains the fibre that diameter is 50 microns
Cellulose fiber；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 200 mesh, and the interval between interval and weft yarn between the warp thread is 75
Micron；
(4) cellulose membrane obtained above is placed in air, measures the contact angle ≈ 0 of nanofiber film surface at this time and watero。
The contact angle ≈ 151 of underwater cellulose membrane and diesel oilo.Oil-water separation mesh film obtained above is fixed on by cellulose membrane later
Among simple glass flange, upper and lower side is respectively feed glass pipe and discharging glass tube, (uses three dyestuff of the Sudan by bavin diesel oil
Oil dye be red liquid) (volume ratio of diesel oil and water is 2:3, must after magnetic agitation 25 minutes with 100 milliliters of the mixture of water
30 microns of the oil droplet size of diesel oil into water) it is poured in above-mentioned oil-water separation mesh film by top feed glass pipe, water passes through oil
Moisture off-network film discharges glass tube outflow from below, while diesel oil is blocked in the upper end of oil-water separation mesh film.Experiment shows can
The purpose of oil water mixture separation is realized in 3.2 minutes, and separation rate is 99.3%.
Embodiment 3
(1) seed culture fluid of preparatory cultured acetobacter xylinum strain is inoculated in 10 litre acetobacters with 13% inoculum concentration
It in fermentation culture, sufficiently vibrates, is statically placed in 30 degrees Celsius of insulating boxs and cultivates 15 days to obtain cellulose aquagel；The wherein wooden vinegar bar
Bacterium fermentation culture contains glucose 2%, and peptone 0.5%, yeast powder 0.5%, five water disodium hydrogen phosphates 0.27%, mass concentration is
Citric acid-hydrate 0.115% of 2.5 grams per liters, pH 6.0, and sterilize 20 minutes under 121 degrees Celsius；Microorganism is sent out
Ferment and the cellulose aquagel come is placed in 5% NaOH aqueous solution 90 degrees Celsius and handles 10 hours, then be placed in 85 in deionized water
Degree Celsius processing 15 hours, during which replace deionized water 3 times, obtain cellulose aquagel block；40 are added in three-necked flask
Ml deionized water and 15 milliliters of concentrated sulfuric acids, magnetic agitation are uniformly mixed.It will be 1.5 centimetres having a size of 1.0 cm x, 1.5 cm x
The cellulose aquagel block that is obtained by above-mentioned steps immerse in acid solution, disperse under the conditions of 80 degrees Celsius and magnetic agitation
1.2 hours, washing dispersion liquid to neutrality obtained the dispersion liquid for the nanofiber that mass fraction of solids is 0.4%；
(2) liquor natrii hypochloritis, volume ratio is added in the cellulose nano-fibrous dispersion liquid prepared to step (1) are as follows: cellulose
Nanofiber dispersion liquid: liquor natrii hypochloritis=100:3 stirs evenly, and glacial acetic acid is added dropwise after reaction 30 minutes to neutrality, 25
Degrees Celsius lower heating stirring 40 minutes, concentration formed the spinning solution that viscosity is 6000 pascal seconds, and spinning solution vacuum filtration is gone
After bubble, temperature be 25 degrees Celsius, relative humidity 45%, winding distance is uses dry spinning device under the conditions of 8-12 centimetres
Extrusion obtains as-spun fibre cellulose fiber；It through wind speed is 0.3 ~ 0.5 metre per second (m/s) by the as-spun fibre cellulose fiber, temperature is 40 ~ 60 to take the photograph
Drawing is blown under the hot wind of family name's degree 10 ~ 15 minutes, it is 100 ~ 120 degrees Celsius of heat in temperature that the twist, which is/10 centimetres of twisting of 400 ~ 600 twirl,
Sizing 5 ~ 10 minutes, then go to twist and obtain the cellulose fibre that diameter is 30 microns；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 300 mesh, and the interval between interval and weft yarn between the warp thread is 50
Micron；
(4) cellulose membrane obtained above is placed in air, measures the contact angle ≈ 0 of nanofiber film surface at this time and watero。
The contact angle ≈ 153 of underwater cellulose membrane and diesel oilo.Cellulose membrane is fixed among simple glass flange later, upper and lower side
Respectively feed glass pipe and discharging glass tube, by n-hexane (being contaminated n-hexane for red liquid using three dyestuff of the Sudan) and water
100 milliliters of mixture (volume ratio of n-hexane and water be 3:7, obtained after twenty minutes through magnetic agitation in water n-hexane oil
Drop partial size is 20~35 microns) it is poured in above-mentioned oil-water separation mesh film by top feed glass pipe, water passes through oil-water separating net
Film discharges glass tube outflow from below, while n-hexane is blocked in the upper end of oil-water separation mesh film, and oil can be realized in 4 minutes
The purpose of aqueous mixtures separation, and separation rate is 99.4%.
Embodiment 4
(1) seed culture fluid of preparatory cultured acetobacter xylinum strain is inoculated in 17 litre acetobacters with 15% inoculum concentration
It in fermentation culture, sufficiently vibrates, is statically placed in 30 degrees Celsius of insulating boxs and cultivates 15 days to obtain cellulose aquagel；The wherein wooden vinegar bar
Bacterium fermentation culture contains glucose 2%, and peptone 0.5%, yeast powder 0.5%, five water disodium hydrogen phosphates 0.27%, mass concentration is
Citric acid-hydrate 0.115% of 2.5 grams per liters, pH 6.0, and sterilize 20 minutes under 121 degrees Celsius；Microorganism is sent out
Ferment and the cellulose aquagel come is placed in 5% NaOH aqueous solution 90 degrees Celsius and handles 10 hours, then be placed in 85 in deionized water
Degree Celsius processing 15 hours, during which replace deionized water 3 times, obtain cellulose aquagel block；40 are added in three-necked flask
Ml deionized water and 10 milliliters of concentrated nitric acids, magnetic agitation are uniformly mixed.It will be 1.5 centimetres having a size of 0.5 cm x, 1.5 cm x
The cellulose aquagel block that is obtained by above-mentioned steps immerse in acid solution, disperse under the conditions of 80 degrees Celsius and magnetic agitation
1 hour, washing dispersion liquid to neutrality obtained the dispersion liquid for the nanofiber that mass fraction of solids is 0.6%；
(2) by the cellulose nano-fibrous dispersion liquid of step (1) preparation through filtering, deaeration, formation temperature is 60 degrees Celsius of spinning
Stoste.The spinning solution is sprayed after metering pump, filter from spinneret orifice later, is that 50 degrees Celsius of coagulating baths are into temperature
The aqueous solution of dimethylformamide, and the concentration of coagulating bath dimethylformamide is 25 ~ 70%, obtains as-spun fibre cellulose fiber.It will
The as-spun fibre cellulose fiber by total stretch ratio be 3 drawing-off, wash, oil, baking process obtains the fibre that diameter is 18 microns
Cellulose fiber；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 400 mesh, and the interval between interval and weft yarn between the warp thread is 30
Micron；
(4) cellulose membrane obtained above is placed in air, measures the contact angle ≈ 0 of nanofiber film surface at this time and watero。
The contact angle ≈ 155 of underwater cellulose membrane and diesel oilo.The cellulose membrane is fixed among simple glass flange later, up and down
End is respectively feed glass pipe and discharging glass tube, by diesel oil (being contaminated diesel oil for red liquid using three dyestuff of the Sudan) and water
100 milliliters of mixture (volume ratio of diesel oil and water be 2:3, after magnetic agitation 25 minutes in water diesel oil oil droplet size be 30~
50 microns) it is poured in above-mentioned oil-water separation mesh film by top feed glass pipe, water passes through oil-water separation mesh film and discharges from below
Glass tube outflow, while diesel oil is blocked in the upper end of oil-water separation mesh film, can realize that oil water mixture separates in 4.3 minutes
Purpose, and separation rate be 99.7%.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It still can carry out and modify to technical solution documented by foregoing embodiments, or carry out to part of technical characteristic
Equivalent replacement, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in
Within protection scope of the present invention.
Claims (4)
1. a kind of super hydrophilic and underwater superoleophobic cellulose membrane, it is characterised in that: pass through mechanical weaving square by warp thread and weft yarn
Method is made, and warp thread and weft yarn are interweaved, and forms the cellulose membrane that mesh number is 50~500 mesh through thermo-compression bonding；The warp thread and
Weft yarn uses diameter for 10~1000 microns of cellulose fibre；The cellulose fibre is by cellulose nano-fibrous passing through
Fiber spinning processes are learned to be made；The interval between interval and weft yarn between the warp thread is 25 ~ 3962 microns.
2. a kind of preparation method of as described in claim 1 super hydrophilic and underwater superoleophobic cellulose membrane, which is characterized in that
The following steps are included:
(1) prepare cellulose nano-fibrous dispersion liquid: prepare solid masses percentage be 0.1~1%, fibre diameter be 1~
300 nanometers of cellulose nano-fibrous dispersion liquid or solid masses percentage is 0.1~1%, fibre diameter is 1~300 to receive
Rice and cellulose nano-fibrous dispersion liquid of the granularity less than 1 centimetre；
(2) to above-mentioned steps (1) preparation cellulose nano-fibrous dispersion liquid use chemical fibre spinning method obtain diameter for
10~1000 microns of cellulose fibre, the chemical fibre spinning method are dry spinning or wet spinning；
The process for wherein preparing cellulose fibre using dry spinning technology is as follows:
Liquor natrii hypochloritis, volume ratio is added in the cellulose nano-fibrous dispersion liquid that (2-1) is prepared to step (1) are as follows: fiber
Plain nanofiber dispersion liquid: liquor natrii hypochloritis=100:1 ~ 5 stirs evenly, and glacial acetic acid is added dropwise after reaction 30 minutes to neutrality,
25 ~ 35 degrees Celsius lower heating stirring 30 ~ 90 minutes, concentration formed viscosity be 5000 ~ 10000 pascal seconds spinning solution, will
After de-soak is filtered by vacuum in spinning solution, temperature be 25 degrees Celsius, relative humidity 45%, winding distance under the conditions of 8-12 centimetres,
It squeezes out to obtain as-spun fibre cellulose fiber using dry spinning device；
The as-spun fibre cellulose fiber that (2-2) prepares step (2-1) through wind speed is 0.3 ~ 0.5 metre per second (m/s), temperature is 40 ~ 60 Celsius
Drawing is blown under the hot wind of degree 10 ~ 15 minutes, the twist is/10 centimetres of twisting of 400 ~ 600 twirl, is that 100 ~ 120 degrees Celsius of heat are fixed in temperature
Type 5 ~ 10 minutes, then go to twist and obtain the cellulose fibre that diameter is 10~1000 microns；
The process for wherein preparing cellulose fibre using wet spinning technology is as follows:
For the cellulose nano-fibrous dispersion liquid that (2-3) prepares step (1) through filtering, deaeration, formation temperature is 15 ~ 120 Celsius
Spend spinning solution；
The spinning solution that (2-4) prepares step (2-3) after metering pump, filter from spinneret orifice spray, into temperature be 20 ~
In 90 degrees Celsius of coagulating baths, coagulating bath be dimethyl acetamide, dimethylformamide, dimethyl sulfoxide aqueous solution in it is any
One kind, and solidifying bath concentration is 25 ~ 70%, obtains as-spun fibre cellulose fiber；
The as-spun fibre cellulose fiber that (2-5) prepares step (2-4) by total stretch ratio be 0.5 ~ 7.0 drawing-off, washing, on
Oil, baking process obtain the cellulose fibre that diameter is 10~1000 microns；
(3) obtain being interweaved by warp thread and weft yarn using mechanical weaving method by the cellulose fibre of above-mentioned steps (2) preparation,
Thermo-compression bonding forms the cellulose membrane that mesh number is 50~500 mesh, and the interval between interval and weft yarn between the warp thread is equal
It is 25 ~ 3962 microns.
3. preparation method as claimed in claim 2, which is characterized in that step (1) prepares cellulose nano-fibrous dispersion liquid,
The first preparation process therein is as follows:
(1-1) mixes sodium hydroxide and urea, mixed mass percent are as follows: sodium hydroxide: urea=1:(0.5~2),
Deionized water is added in mixture, is uniformly mixing to obtain the first solution, wherein sodium hydroxide account for total solution mass percent 4~
8%；
Commercial plant cellulose is added in above-mentioned first solution by (1-2) under conditions of mechanical stirring, the quality hundred of addition
Divide ratio are as follows: plant cellulose powder: the first solution=1:(25~100), obtain mixed solution；By the mixed solution temperature be 0
It places 3~8 hours, takes out under~-20 degrees celsius, it is molten to obtain second after stirring 15~30 minutes under normal temperature and pressure conditions
Liquid；Ethyl alcohol or methanol are added in the second solution, the volume ratio of addition are as follows: ethyl alcohol or methanol: the second solution=1:(0.7~
1.4) after, standing 0.4~0.7 hour, 2~5 solvent replacements is carried out with isometric deionized water of the second solution, obtain solid
The cellulose nano-fibrous dispersion liquid that mass percent is 0.1~1%, fibre diameter is 1~300 nanometer.
4. preparation method as claimed in claim 2, which is characterized in that step (1) prepares cellulose nano-fibrous dispersion liquid,
Second of preparation process is as follows:
(1-3) prepares acetobacter xylinum fermentation culture: the mass percent of acetobacter xylinum fermentation culture are as follows: glucose 2%, egg
White peptone 0.5%, yeast powder 0.5%, five water disodium hydrogen phosphates 0.27%, mass concentration are no more than citric acid-hydrate of 3 grams per liters
0.115%, pH value is to sterilize 20 minutes under 4~6,121 degrees Celsius, is sufficiently vibrated；By the seed training of commercial acetobacter xylinum strain
Nutrient solution is inoculated into above-mentioned acetobacter xylinum fermentation culture, and the seed culture fluid of acetobacter xylinum strain is acetobacter xylinum fermented and cultured
It is cultivated 15 days under 30 degrees Celsius sufficiently after oscillation, obtains cellulose aquagel in the 8~25% of liquid quality；By cellulose water-setting
Glue is placed in the NaOH aqueous solution that molar concentration is 5%, is heated to 90 degrees Celsius, keeps the temperature 10 hours, then be placed in deionized water,
15 hours are kept the temperature under 85 degrees Celsius, obtains cellulose aquagel block；
Above-mentioned cellulose aquagel block is put into sulfuric acid, hydrochloric acid, nitric acid, the hydrogen that molar concentration is 3~10 mol/Ls by (1-4)
In any one in bromic acid, hydroiodic acid, it is dispersed with stirring under 60~90 degrees Celsius 0.3~2 hour, is washed with deionized water,
Make solution to neutrality, obtains that solid masses percentage is 0.1~1%, fibre diameter is 1~300 nanometer cellulose nano-fibrous
Dispersion liquid；
Or: above-mentioned cellulose aquagel block is put into mechanical crusher, after deionized water is added, Mechanical Crushing at normal temperature
After 3~8 minutes, obtain that solid masses percentage is 0.1~1%, fibre diameter is 1~300 nanometer and granularity is less than 1 centimetre
Cellulose nano-fibrous dispersion liquid.
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