CN106422421B - A kind of method and application of paper modification preparation water-oil separationg film - Google Patents
A kind of method and application of paper modification preparation water-oil separationg film Download PDFInfo
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- CN106422421B CN106422421B CN201610485203.3A CN201610485203A CN106422421B CN 106422421 B CN106422421 B CN 106422421B CN 201610485203 A CN201610485203 A CN 201610485203A CN 106422421 B CN106422421 B CN 106422421B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0421—Rendering the filter material hydrophilic
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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
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Abstract
The present invention relates to the methods and application of a kind of paper modification preparation water-oil separationg film, using common qualitative filter paper as substrate, by the adhesive attraction of poly-dopamine, mediate layer in surface building PDA.Then the amino of polyethylene glycol or amphoteric ion polymer and PDA mediation layer surface with active ester group is fixed on surface by amidation covalence graft, the hydrophily that modified surface is improved with the hydrophilic interaction of PEG chain segment and its terminal hydroxyl or amphoteric ion polymer, can carry out water-oil separating well.By this method construct water-oil separationg film have hydrophilic/oleophobic characteristic, film have significant antifouling property, can for a long time or reuse the advantages of.
Description
Technical field
The present invention relates to the methods and application of a kind of paper modification preparation water-oil separationg film.
Background technique
Either environmental improvement, oil recovery and sewage treatment recycle, and require and are effectively separated to oily wastewater.
Oily existing forms can be divided into 4 classes in oily wastewater: oily partial size is greater than 150 μm, referred to as oil slick；Oil slick is easily formed in the water surface
Oil film can be separated oil by gravity from sewage.The partial size of oil referred to as disperses between 20 μm~150 μm
Oil；Dispersed oil is unstable, can assemble to form biggish oil droplet and be converted into oil slick after standing a period of time, processing method is more simple
It is single.The partial size of oil is difficult to merge less than 20 μm, referred to as oil emulsion between oil emulsion elaioleucite, is not easy to float on surface, therefore handle
Get up the most difficult.Membrane separation technique is generallyd use to reach water-oil separating.
Water-oil separationg film can be divided into hydrophilic film and hydrophobic membrane, study at present and what application was more is hydrophobic membrane.About grease
Substrate selected by the research of seperation film is mostly the metal grills such as copper mesh, stainless steel and polymer film, nylon cloth etc., using electricity
Burn into immersion, Electrospun and chemical reaction etc. form nanostructured surface or parent/hydrophobic coating.Hydrophobic film is usually by gathering
The polyolefin polymers such as ethylene, Kynoar and polytetrafluoroethylene (PTFE) composition, goes working well for a small amount of water impurity in oil removing,
But it is easy to pollute film seriously, reusable rate is low.In addition, oil molecule is easy to coalesce in hydrophobic membrane and water is prevented to pass through,
Decline water flux sharply.To enable oil quickly to leave film surface, preventing fouling membrane, holding water flux, the surface chemistries of film
Matter should be hydrophilic.Hydrophilic film water flux is high, and contamination resistance is strong, gradually becomes the main membrane material of oily wastewater oil removing operation
Material.
The main composition of filter paper is cellulose, and surface has countless micron order apertures to pass through for liquid.It is repaired on its surface
Nanoscale particle on decorations, and reduce its surface free energy and can reach super-hydrophobic state as water-oil separating material.It is right at present
In filter paper modification mainly be modified as hydrophobic surface (Applied Surface Science, 2012, 258
(22): 8739-8746；ACS Appl. Mater. Interfaces, 2010, 2(3) : 677-683;Applied chemistry,
2012,29 (3): 297-303.).Wherein Chinese patent CN102797197A, CN103993510A, CN104005280A,
CN104018392A and CN104492276A is also to carry out hydrophobically modified to filter paper.But hydrophobically modified presence is carried out to surface
The disadvantages of film is easy to pollute, water flux decaying is very fast, therefore hydrophilic modifying is carried out to surface can overcome as hydrophobicity table
The shortcomings that face, has great practical value in terms of water-oil separating.
Summary of the invention
, water flux easy to pollute for film existing for current hydrophobicity water-oil separationg film decaying is very fast, the reusable rate of film
The problems such as poor, the purpose of the present invention is to provide the methods and application of a kind of paper modification preparation water-oil separationg film.
Realization process of the invention is as follows:
Filter paper immersion aqueous dopamine solution forms its surface poly- by a kind of method of paper modification preparation water-oil separationg film
Then DA Mediated layer is infiltrated the polyethylene glycol or amphoteric ion polymer solution of the group containing active ester, washed
Water-oil separationg film is obtained after drying,
The molecular weight polyethylene glycol of the group containing active ester is 2000 ~ 20000, and structural formula is as follows:
, wherein the positive integer that n is 35 ~ 450；
The amphoteric ion polymer general structure of the group containing active ester are as follows:
Wherein, the integer that x is 10 ~ 800, the integer that y is 5 ~ 600；The mole percent of x is moles the hundred of 70% ~ 90%, y
Score is 10% ~ 30%；R1、R2For-H or-CH3；
W is the small molecule containing amphoteric ion group, and amphoteric ion group is Phosphorylcholine group, carboxylic acid glycine betaine group
Or sulphonic acid betaine group；
Z is active ester group, structural formula are as follows:, a be 1 ~ 30 natural number.
Specifically, the method for above-mentioned paper modification preparation water-oil separationg film, includes the following steps:
(1) filter paper and aqueous dopamine solution are contacted into 1 ~ 6 h of dip-coating, automatically formed in surface with 1 ~ 20 nm thickness
The poly-dopamine of degree mediates layer；
(2) with the polyethylene glycol or amphoteric ion polymer solution of the pH buffer preparation group containing active ester for being 6 ~ 8；
(3) filter paper being modified by dopamine is immersed in the polyethylene glycol or zwitterion polymerization of the group containing active ester
In object solution, make the active ester group of hydrophilic polymer and poly-dopamine coating amino that amidation process occur, by hydrophilic polymeric
Object covalent bonding is in surface；
(4) distilled water of the filter paper after reaction is eluted and removes unreacted completely or combines after hydrophilic polymer loosely
To paper modification water-oil separationg film.
In step (1), the dopamine solution concentration is 0.5 ~ 5 mg/mL, and pH is 6 ~ 9；The dopamine solution
After dip-coating, continues slow reaction 2 days or more in air at room temperature after taking out filter paper, form the poly-dopamine coating of stable bond；
The dopamine solution contains one of potassium peroxydisulfate, ammonium persulfate, copper sulphate and hydrogen peroxide or several as oxidant.
In step (2), the polyethylene glycol or amphoteric ion polymer solution concentration of the group containing active ester are 0.5 ~ 3 mg/
mL。
In step (3), the amidation process temperature is 30 DEG C ~ 80 DEG C；Reaction time is 6 ~ 24 h.
The water-oil separationg film of above method preparation is applied in water-oil separating or oil slick contaminated filter removing field.
Advantages of the present invention and good effect: the present invention passes through the Universal adhesive of dopamine using common qualitative filter paper as substrate
Attached effect is securely fixed in surface building and mediates layer, then one end is had to the polyethylene glycol (HO- of active ester groups
PEG-NHS) or amphoteric ion polymer passes through and DOPA amine layer mediates the deamination effect of layer surface to be grafted on surface, leads to
The hydrophilic ability for crossing PEG chain segment and its terminal hydroxyl and amphoteric ion polymer improves the hydrophily of filter paper, formed it is hydrophilic it is permeable,
The water-oil separationg film for hating oil, can preferably carry out water-oil separating.It is easy to solve film existing for hydrophobicity water-oil separationg film
Pollution, water flux decaying is very fast, film is repeatable.
Figure of description
For Fig. 1 using filter paper as substrate, PDA and HO-PEG-NHS construct water-oil separating membrane structure diagram；
Fig. 2 is rear filter paper comparison diagram before modified；
Fig. 3 is gasoline/aqueous mixtures of emulsification；
Fig. 4 is oil water separation process；
Fig. 5 is that different filter paper separate gasoline/water-in-oil emulsion effect picture；
Fig. 6 is photo after different modified filter paper water-oil separatings.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below, but not as a limitation of the invention.
1 HO-PEG2000-NHS modifying common filter paper of embodiment constructs water-oil separationg film
(1) common qualitative filter paper and the pH aqueous dopamine solution for being 6.9 are contacted into 6 h of dip-coating, in the automatic shape of surface
Layer is mediated at grayish poly-dopamine.8 h under 40 DEG C of air environments are put into, the poly-dopamine coating of stable bond is formed；
(2) with polyethylene glycol (molecular weight 2000, referred to as HO- of the pH buffer preparation group containing active ester for being 7
PEG2000-NHS solution), polyglycol solution concentration are 2 mg/mL.Structural formula is as follows:
Wherein, the natural number that n is 40 ~ 50, active ester group in peg molecule are as follows:；
(3) at 40 DEG C, the filter paper being modified by dopamine is immersed in the polyglycol solution of the group containing active ester
In, 18 h are reacted, make active ester group and poly-dopamine coating amino that amidation process occur, by hydrophilic polymer covalent bonding
In surface, reaction process is as shown in Figure 1；
(4) distilled water of the filter paper after reaction is eluted and removes unreacted completely or combines straight after hydrophilic polymer loosely
It connects for water-oil separating；
(5) it will be measured after the filter paper natural drying at room temperature after distilled water leaching in (4) for photograph and Static water contact angles.
2 HO-PEG10000-NHS modifying common filter paper of embodiment constructs water-oil separationg film
(1) common qualitative filter paper and the pH aqueous dopamine solution for being 7.5 are contacted into 6 h of dip-coating, in the automatic shape of surface
Layer is mediated at grayish poly-dopamine.8 h under 40 DEG C of air environments are put into, the poly-dopamine coating of stable bond is formed；
(2) with the polyethylene glycol 10000 (HO-PEG10000- of the pH buffer preparation group containing active ester for being 6.5
NHS solution), polyglycol solution concentration are 2.5 mg/mL.Structural formula is as follows:
, wherein n be 200 ~ 220 positive integer；
(3) at 40 DEG C, the filter paper being modified by dopamine is immersed in the polyglycol solution of the group containing active ester
In, 18 h are reacted, make active ester group and poly-dopamine coating amino that amidation process occur, by hydrophilic polymer covalent bonding
In surface；
(4) distilled water of the filter paper after reaction is eluted and removes unreacted completely or combines straight after hydrophilic polymer loosely
It connects for water-oil separating；
(5) it will be measured after the filter paper natural drying at room temperature after distilled water leaching in (4) for photograph and Static water contact angles, it is quiet
State contact angle is 3 °.
The modified filter paper of embodiment 3 is tested for the property and water-oil separating experiment
Contact angle test is carried out to the modification filter paper prepared in embodiment 1.Modified filter paper static contact angle is 4 °, illustrates this
The filter paper that preparation method obtains has Superhydrophilic.Filter paper comparison diagram is as shown in Figure 2 after before modified.
Embodiment 4 carries out the experiment of water-oil separating performance to the filter paper that embodiment 1 has been modified
Water-oil separating experiment is carried out using modified filter paper.The preparation method of oil emulsion is as described in Table 1.Fig. 3 is to have emulsified
Gasoline/aqueous mixtures, Fig. 4 be with modification filter paper carry out oil water separation process.
1 oil-water emulsion liquid and preparation method thereof of table
Water-oil separating efficiency is calculated according to formula (1), calculates water-oil separating efficiency.The water-oil separating effect being calculated
Rate is as shown in table 2.Water phase after separation is as shown in figure 4, filtered filter paper (hygrometric state) is as shown in Figure 6.By table 2 and Fig. 5, Fig. 6
It can be seen that the modification filter paper through the method for the present invention preparation has preferable separative efficiency and filter paper is not easy to be contaminated, there is weight
Big application value.
The separative efficiency of the different oil-water mixtures of table 2
As shown in Table 2, the separative efficiency of different oil/water emulsions is up to 99.9% or more.
The amphoteric ion polymer of the group containing active ester of embodiment 5 prepares water-oil separationg film
Preparation method the following steps are included:
(1) filter paper and the pH aqueous dopamine solution for being 8.5 are contacted into 4 h of dip-coating, automatically forms light gray in surface
Poly-dopamine mediate layer.It takes out to be placed in air at room temperature and dry, form the poly-dopamine coating of stable bond；
(2) the amphoteric ion polymer solution that the group containing active ester is prepared with dehydrated alcohol adjusts pH value to 7.0；
(3) at 60 DEG C, the filter paper being modified by dopamine is immersed in the zwitterion polymerization of the group containing active ester
In object solution, 6 h are reacted, make active ester group and poly-dopamine coating amino that amidation process occur, by hydrophilic polymer
Covalent bonding is in surface, general structure are as follows:
Wherein, the integer that x is 10 ~ 800, the integer that y is 5 ~ 600；The mole percent of x is moles the hundred of 70% ~ 90%, y
Score is 10% ~ 30%；R1、R2For-H or-CH3；
W is the small molecule containing amphoteric ion group, and amphoteric ion group is Phosphorylcholine group, carboxylic acid glycine betaine group
Or sulphonic acid betaine group is one such or several；
Z is active ester group, structural formula are as follows:, a be 1 ~ 30 natural number；
(4) distilled water of the filter paper after reaction is eluted and removes unreacted completely or combines straight after hydrophilic polymer loosely
It connects for water-oil separating；
(5) the modification filter paper after above-mentioned elution is saved after drying at room temperature, carries out water-oil separating after being soaked with water.
Embodiment 6
Contact angle test and water-oil separating experiment are carried out to the hydrophily filter paper prepared in embodiment 5.
According to modification filter paper prepared by embodiment 5, there is Superhydrophilic, static contact angle is 2 °.Utilize modified filter paper
Carry out water-oil separating experiment.With described in embodiment 4, table 3 is oil mixing with water for the preparation method of emulsion, water-oil separating experimental method
The separative efficiency of liquid.
The separative efficiency of the different oil-water mixtures of table 3
As shown in Table 3, have according to the water-oil separationg film prepared using filter paper as substrate prepared in the present embodiment compared with great number
Separative efficiency.Meanwhile filter paper is carried out after experiment to carry out water-oil separating, separative efficiency base again after simply rinsing with distilled water
This nothing is obviously reduced, and illustrates that the water-oil separationg film contamination resistance prepared according to the method for the present invention is strong.
Claims (8)
1. a kind of method of paper modification preparation water-oil separationg film, it is characterised in that: filter paper immersion aqueous dopamine solution is made it
Surface forms poly-dopamine and mediates layer, the polyglycol solution of the group containing active ester is then infiltrated, after washed drying
Water-oil separationg film is obtained,
The molecular weight polyethylene glycol of the group containing active ester is 2000 ~ 20000, and structural formula is as follows:
, wherein the positive integer that n is 35 ~ 450.
2. the method for paper modification preparation water-oil separationg film according to claim 1, it is characterised in that include the following steps:
(1) filter paper and aqueous dopamine solution are contacted into 1 ~ 6 h of dip-coating, automatically formed in surface with 1 ~ 20 nm thickness
Poly-dopamine mediates layer；
(2) with the polyglycol solution of the pH buffer preparation group containing active ester for being 6 ~ 8；
(3) filter paper being modified by dopamine is immersed in the polyglycol solution of the group containing active ester, makes hydrophilic polymeric
Amidation process occurs for the active ester group and poly-dopamine coating amino of object, by hydrophilic polymer covalent bonding in filter paper table
Face；
(4) filter paper after reaction is eluted with distilled water and removes unreacted and is filtered completely or after combining hydrophilic polymer loosely
Paper is modified water-oil separationg film.
3. the method for paper modification preparation water-oil separationg film according to claim 2, it is characterised in that: described in step (1)
Dopamine solution concentration be 0.5 ~ 5 mg/mL, pH be 6 ~ 9.
4. the method for paper modification preparation water-oil separationg film according to claim 2, it is characterised in that: described in step (1)
Dopamine solution dip-coating after, take out filter paper after continues slow reaction 2 days or more in air at room temperature, formed stable bond gather
Dopamine coating.
5. according to the method described in claim 2, it is characterized by: the dopamine solution contains persulfuric acid in step (1)
One of potassium, ammonium persulfate, copper sulphate and hydrogen peroxide are several as oxidant.
6. according to the method described in claim 2, it is characterized by: in step (2), the polyglycol solution of the group containing active ester
Concentration is 0.5 ~ 3 mg/mL.
7. according to the method described in claim 2, it is characterized by: the amidation process temperature is 30 DEG C in step (3)
~80℃；Reaction time is 6 ~ 24 h.
8. the water-oil separationg film prepared using method described in claim 1 removes field in water-oil separating or oil slick contaminated filter
Middle application.
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| CN108250477B (en) * | 2018-01-26 | 2021-04-06 | 中国科学院长春应用化学研究所 | Modified SEBS material and preparation method and application thereof |
| CN108822326B (en) * | 2018-06-08 | 2021-06-04 | 西北大学 | Zwitterionic copolymer, preparation method and method for constructing coating by utilizing zwitterionic copolymer |
| CN108815882B (en) * | 2018-06-15 | 2020-05-29 | 山东交通学院 | Bionic oil-water separation material with antifouling, sterilizing and dye adsorption functions and preparation method thereof |
| CN109011706B (en) * | 2018-08-27 | 2021-02-09 | 济南大学 | Preparation method and application of super-oleophobic polyurea-cellulose material |
| CN109091914B (en) * | 2018-08-27 | 2021-04-23 | 济南大学 | Preparation method and application of super-hydrophobic polyurea-cellulose composite material |
| CN110201551B (en) * | 2019-05-08 | 2021-09-28 | 西南石油大学 | Self-cleaning nano cellulose membrane for oil-water separation, preparation method and application thereof |
| CN110670056B (en) * | 2019-10-10 | 2021-06-01 | 泉州师范学院 | Polyasparagine derivative modified oil-water separation stainless steel net film and preparation method thereof |
| CN112691550A (en) * | 2019-10-21 | 2021-04-23 | 中国石油化工股份有限公司 | Method for preparing anti-pollution modified ion exchange membrane |
| CN112759041A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing anti-pollution ion exchange membrane |
| CN113559555B (en) * | 2021-07-29 | 2023-03-21 | 华东理工大学 | Block polymer modified oil-water separation stainless steel mesh and preparation method thereof |
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