CN105727596B - A kind of porous material of Polyaniline-modified and its application - Google Patents
A kind of porous material of Polyaniline-modified and its application Download PDFInfo
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- CN105727596B CN105727596B CN201610192613.9A CN201610192613A CN105727596B CN 105727596 B CN105727596 B CN 105727596B CN 201610192613 A CN201610192613 A CN 201610192613A CN 105727596 B CN105727596 B CN 105727596B
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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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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of porous material of Polyaniline-modified, the porous material is prepared by the following method to obtain：Electrolyte is used as using 0.1M aniline sulfuric acid solution, stainless (steel) wire is as working electrode, platinum plate electrode is used as to electrode, saturated calomel electrode is as reference electrode, polyaniline-coated is grown in the surface of stainless (steel) wire under 25 35 DEG C of constant temperatures using cyclic voltammetry, then stainless (steel) wire is taken out and cleaned with the ammonia spirit that pH is 10, dried；Cyclic voltammetry is in two steps：The first step is circulated 46 times using 0.2V 1.0V overpotential, until there is low current peak on cyclic voltammetry curve；Second step uses 0.2V 0.9V potential cycles 10 25 times.The invention also discloses application of the porous material in high surfactant oil-in-water emulsion and water-in-oil emulsion two-phase laminated flow.The porous material of Polyaniline-modified of the present invention has excellent stain resistance and recycles performance, and stability is good.
Description
Technical field
The present invention relates to a kind of porous material of Polyaniline-modified and its application, belongs to process for modifying surface field.The material
Material is available for oil-in-water emulsion and the two-phase laminated flow of water-in-oil emulsion.
Background technology
With industrial development and the quickening of urbanization process, the discharge of trade effluent and sanitary wastewater aggravates, so as to give
River causes huge pollution；In addition, Activities of Ocean it is increasing such as：The exploitation of offshore oil and leakage accident, ship
Waste gas and discharge of wastewater etc. also result in marine pollution, and oily waste water is wherein main pollution sources.In view of the whole world is drunk
Water water scarcity and marine environment ecological disruption are serious, realize oily waste water especially oil-in-water emulsion purified treatment and then
Realize that purifying dirty water reuse tool is of great significance.
Meanwhile the high speed development of modern industry, the huge thrust of blood-oil of too busy to get away industry.The exploitation of oil,
The links transport, store, used are required for refining meticulously.And when exploitation crude oil water containing can be to crude oil production, crude oil outside
The processing of defeated and refinery can all bring larger harm.Crude oil water containing can increase the volume of oil well produced liquid, reduce equipment and
The effective rate of utilization of pipeline；Crude oil water containing can increase the fuel consumption in power consumption and temperature-rise period in Pipeline transport；
In addition, crude oil water containing can cause the fouling and corrosion of metallic conduit and refining equipment, the safety for causing the transport of crude oil to refine is hidden
Suffer from.Meanwhile the petrol and diesel oil and lubricating oil used once contains moisture, corrosion can be caused to further result in component wear engine
Aggravation.Based on this, the purification of wet crude is a highly important problem, also complies with the theory of people's environmental protection and energy saving instantly.
Realize the purified treatment of oily waste water and the purification of wet crude, be exactly by water-oil phase mixture oil with
Water is separated by external force.Traditional oil-water separation method includes gravitational method, centrifugal process, the way of distillation, chemical method etc..But this
A little methods are not only needed to consume energy but also waste time and energy, complex operation, and large-scale separation is locked into toward contact.Membrane separating method by
Simple and easy in its, cheap, the advantage such as pollution-free has obtained extensive concern.Microfiltration membranes, NF membrane and milipore filter are in oil
Starts gradually to apply for everybody in water separation especially emulsion separation, but flow velocity to be present low for these films, it is easily contaminated, so as to
The defects of causing its service life short.
In the last few years, with special wetability thin-film material while realizing that water-oil phase mixture efficiently separates not
The pollution of film can be caused and keep higher flow velocity to be increasingly becoming a study hotspot.It is and currently thin with special wetability
Film can only realize the purification of oily waste water or the purification of wet crude merely, and both realities simultaneously on same film
Now also it is rarely reported.
The content of the invention
It is an object of the invention to provide a kind of porous material of Polyaniline-modified and its application.The present invention uses electrochemistry
It polymerize polyaniline（PANI）Method in porous material-stainless (steel) wire（SSM）The strata aniline nano-fiber material of Surface coating one,
Wherein by adjusting electrochemical polymerization parameter, realize that polyaniline-coated thickness is adjustable and the aperture of stainless (steel) wire is controllable, finally
Thin-film material super-hydrophobic under super hydrophilic-underwater superoleophobic while super oleophylic-oil is obtained using AMMONIA TREATMENT.
A kind of porous material of Polyaniline-modified, it is characterised in that the porous material is prepared by following steps：
1）0.1M aniline-sulfuric acid solution is prepared with 1M sulfuric acid solution；
2）Stainless (steel) wire is cleaned by ultrasonic with ethanol, acetone, distilled water immersion successively, drying for standby；
3）0.1M aniline-sulfuric acid solution is used as to electricity as electrolyte, stainless (steel) wire as working electrode, platinum plate electrode
Pole, saturated calomel electrode are grown polyaniline-coated using cyclic voltammetry under 25-35 DEG C of constant temperature as reference electrode
On the surface of stainless (steel) wire, then stainless (steel) wire is taken out and cleaned with the ammonia spirit that pH is 10, is dried；
The cyclic voltammetry is in two steps：First step use -0.2V-1.0V overpotential circulates 4-6 times, until cyclic voltammetric
Occurs low current peak on curve；Second step use -0.2V-0.9V potential cycles 10-25 times.
The mesh number of the stainless (steel) wire is the mesh of 1000 mesh -3000.
The porous material of above-mentioned Polyaniline-modified is used for the two-phase of high surfactant oil-in-water emulsion and water-in-oil emulsion
Separation.
Separation of the porous material of the Polyaniline-modified for high surfactant Tween80 oil-in-water emulsion.
Separation of the porous material of the Polyaniline-modified for high surfactant Span80 water-in-oil emulsion.
First step use -0.2V-1.0V overpotential circulates 4-6 times in cyclic voltammetry, until going out on cyclic voltammetry curve
Existing low current peak, shows that there is polyaniline generation on surface；Second step use -0.2V-0.9V potentials in cyclic voltammetry, time of circulation
Number is 10-25 times, using low-voltage current peak can be made slowly to increase, and then the effective polyaniline that suppresses is in stainless steel netlist
The ultra-rapid growth in face so that the uniform compact (note of surface polyaniline-coated：Described cycle-index is followed all referring to second step below
Ring number).
Compared with prior art, the advantage of the invention is that：
1st, present invention process is simple, and raw material is easy to get, and cost is low.
2nd, the present invention is by adjusting electrochemical polymerization parameter, realizes that polyaniline-coated thickness is adjustable and the hole of stainless (steel) wire
Footpath is controllable.
3rd, the porous material of Polyaniline-modified of the present invention has special wetability, at the same have concurrently it is underwater superoleophobic and
It is super-hydrophobic in oil.
4th, the porous material of Polyaniline-modified of the present invention can realize oil-in-water emulsion and water-in-oil emulsion simultaneously
Efficient quick separating.
5th, the porous material of Polyaniline-modified of the present invention has excellent stain resistance and recycles performance, stable
Property is good.
Brief description of the drawings
Fig. 1 is the 2300 mesh stainless (steel) wires coated in the embodiment of the present invention 1 using the PANI of different cyclic voltammetric numbers
ESEM（SEM）Photo, wherein a are the electromicroscopic photographs of original stainless (steel) wire, b, c and d be respectively circulation 5,10,18 times
The photo of stainless (steel) wire after Polyaniline-modified.
Fig. 2 is the wetability of different 0 time, the 5 times and 10 times polyaniline-coated stainless (steel) wire of cycle-index of the embodiment of the present invention 1
Change.Figure a is the contact angle of different oil droplets under water；Figure b is the contact angle in different organic solvents reclaimed water.Wherein N：16
Alkane；P:Petroleum ether；H：N-hexane；C：Chloroform；D：Dichloroethanes.
Fig. 3 is the contact angle and roll angle for the polyaniline-coated stainless (steel) wire for circulating 18 times.It is 18 polyaniline-coateds to scheme a
Stainless (steel) wire in water the contact angle of different oil droplets and in different organic solvents water droplet contact angle；Figure b be circulation 10 times and
The roll angle of 18 water droplets in n-hexane and in water dichloroethanes roll angle.Wherein N：Hexadecane；P:Petroleum ether；H：Just
Hexane；C：Chloroform；D：Dichloroethanes.
Fig. 4 is that the polyaniline-coated stainless (steel) wire for circulating 10 times and 18 times is utilized in the embodiment of the present invention 1 to three kinds of water bags
The separating rate and Efficiency testing of fat liquor and three kinds of water-in-oil emulsions.Figure a is stainless using the polyaniline-coated of 10 circulations
Steel mesh filters three kinds of oil-in-water emulsions of separation with the polyaniline-coated stainless (steel) wire of 18 circulations under 0.1bar under gravity；Figure
B is the polyaniline-coated stainless (steel) wire of 10 circulations under gravity with 18 polyaniline-coated stainless (steel) wires circulated in 0.1bar
It is lower to filter three kinds of water-in-oil emulsions of separation；Figure c is the content COD value of the Organic substance in water after being separated in detection figure a；Figure d is inspection
The content of Water in Organic Solvents point after mapping b separation.Wherein N：Hexadecane；P:Petroleum ether；H：N-hexane；C：Chloroform；
D：Dichloroethanes.
Fig. 5 is that the optics that three kinds of oil-in-waters and three kinds of water-in-oil emulsions are separated using 18 polyaniline-coated stainless (steel) wires is shone
Piece and its corresponding microphotograph.Figure a, c, e are water bag n-hexane, water bag petroleum ether, the separation of water bag hexadecane emulsion respectively
Front and rear optics and microphotograph；It is n-hexane Bao Shui, chloroform Bao Shui, dichloroethanes bag aqueous emulsion respectively to scheme b, d, f
Separation front and rear optics and microphotograph.
Embodiment
Embodiment 1
（1）The processing of substrate：
2300 mesh stainless (steel) wire ethanol, acetone, distilled water are respectively cleaned by ultrasonic 3 times, 60 DEG C of oven dryings are stand-by.
（2）Polyaniline-modified：
70mL 0.1M aniline-sulfuric acid solution is measured as electrolyte, stainless (steel) wire（2.5cm*3cm）As work electricity
Pole, platinum plate electrode（1cm*1cm）As to electrode, saturated calomel electrode is as reference electrode.In thermostat water bath（30℃）In,
Circulated respectively using cyclic voltammetry 5,10,18 times, polyaniline polymerization cladding is grown in the surface of stainless (steel) wire, finally taken
Go out, cleaned, dried with the ammonia spirit that pH is 10.The film scanning Electronic Speculum being prepared is as shown in Figure 1.
（3）The stainless (steel) wire for circulating Polyaniline-modified made from 10 times and 18 times is filtered in gravity and its 0.1bar respectively
0.1mg/mL Tween80 water bags n-hexane, three kinds of oil-in-water emulsions of petroleum ether and hexadecane and 2 mg/mL are separated under pressure
The separation of n-hexane, dichloroethanes and chloroform Bao Shuisan kind water-in-oil emulsions, its flow velocity and its separation existing for Span80
Efficiency is respectively as shown in figure 4, optical photograph and its microphotograph illustrate three kinds of oil-in-water emulsions and three kinds as shown in Figure 5 simultaneously
Water-in-oil emulsion system can be separated fast and effectively.Illustrating the stainless (steel) wire for the Polyaniline-modified that we prepare has
Versatility and intelligent.There is good application prospect in the purification of oily waste water and the purification processes of wet crude.
Claims (4)
1. a kind of porous material of Polyaniline-modified, it is characterised in that the porous material is prepared by following steps：
1）0.1M aniline-sulfuric acid solution is prepared with 1M sulfuric acid solution；
2）The mesh stainless (steel) wire of 1000 mesh -3000 is cleaned by ultrasonic with ethanol, acetone, distilled water immersion successively, drying for standby；
3）0.1M aniline-sulfuric acid solution is as electrolyte, and as working electrode, platinum plate electrode is used as to electrode stainless (steel) wire,
Polyaniline-coated is grown in by saturated calomel electrode as reference electrode under 25-35 DEG C of constant temperature using cyclic voltammetry
The surface of stainless (steel) wire, then stainless (steel) wire is taken out and cleaned with the ammonia spirit that pH is 10, is dried；
The cyclic voltammetry is in two steps：First step use -0.2V-1.0V overpotential circulates 4-6 times, until cyclic voltammetry curve
On there is low current peak；Second step use -0.2V-0.9V potential cycles 10-25 times.
2. the porous material of Polyaniline-modified as claimed in claim 1 is in high surfactant oil-in-water emulsion and water-in-oil emulsion
Application in two-phase laminated flow.
3. application as claimed in claim 2, it is characterised in that the porous material of the Polyaniline-modified is used for high surface
The separation of agent Tween80 oil-in-water emulsion.
4. application as claimed in claim 2, it is characterised in that the porous material of the Polyaniline-modified is used for high surface
The separation of agent Span80 water-in-oil emulsion.
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| CN111266018B (en) * | 2020-02-12 | 2021-05-11 | 中国科学院生态环境研究中心 | Polymer film with adjustable wettability as well as preparation method and application thereof |
| CN114735793B (en) * | 2022-04-14 | 2023-01-17 | 陕西科技大学 | Application of sulfuric acid doped polyaniline modified carbon fiber electrode in removal of nitrate in water through electro-catalytic reduction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544702A (en) * | 2003-11-21 | 2004-11-10 | ���Ŵ�ѧ | Process for preparing carbon supported polymer surface nano-alloy electrocatalytic electrode |
| CN101034627A (en) * | 2007-04-19 | 2007-09-12 | 北京科技大学 | Multi-hole casting carbon/polyaniline super capacitor electrode material and its preparing method |
| CN101740228A (en) * | 2009-12-23 | 2010-06-16 | 南京航空航天大学 | Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel |
| CN102416269A (en) * | 2011-08-23 | 2012-04-18 | 北京航空航天大学 | Micro/nano interface separation net as well as preparation method and application thereof |
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN105148619A (en) * | 2015-08-19 | 2015-12-16 | 中国科学院兰州化学物理研究所 | Method for preparing polyaniline modified porous material |
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- 2016-03-30 CN CN201610192613.9A patent/CN105727596B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544702A (en) * | 2003-11-21 | 2004-11-10 | ���Ŵ�ѧ | Process for preparing carbon supported polymer surface nano-alloy electrocatalytic electrode |
| CN101034627A (en) * | 2007-04-19 | 2007-09-12 | 北京科技大学 | Multi-hole casting carbon/polyaniline super capacitor electrode material and its preparing method |
| CN101740228A (en) * | 2009-12-23 | 2010-06-16 | 南京航空航天大学 | Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel |
| CN102416269A (en) * | 2011-08-23 | 2012-04-18 | 北京航空航天大学 | Micro/nano interface separation net as well as preparation method and application thereof |
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN105148619A (en) * | 2015-08-19 | 2015-12-16 | 中国科学院兰州化学物理研究所 | Method for preparing polyaniline modified porous material |
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