CN105926020A - Preparation method for super-hydrophilic foam titanium used for oil-water separation - Google Patents

Preparation method for super-hydrophilic foam titanium used for oil-water separation Download PDF

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CN105926020A
CN105926020A CN201610421063.3A CN201610421063A CN105926020A CN 105926020 A CN105926020 A CN 105926020A CN 201610421063 A CN201610421063 A CN 201610421063A CN 105926020 A CN105926020 A CN 105926020A
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preparation
titanium
oil
titanium foam
foam
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CN105926020B (en
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莫冬传
罗智勇
吕树申
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National Sun Yat Sen University
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National Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Water Treatments (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a preparation method for super-hydrophilic foam titanium used for oil-water separation. The preparation method includes the three steps of material pretreatment, anode oxidizing treatment and ultraviolet radiation. The surface of the obtained foam titanium is composed of intrinsic hydrophilic fluorine titanium oxide and is covered with countless nano-cavities at the same time, the roughness coefficient Rq reaches 35.6 nm, and the hydrophilic performance of the surface of the foam titanium can be further enhanced. The foam titanium has good super-hydrophilicity and underwater super-oleophobicity, the water drop contact angle in air is 0 degree, the underwater oil contact angle is 160 degrees, and a good oil-water separation effect is achieved. When the filter fineness reaches 20 micrometers or below, the foam titanium can further be used for emulsion separation, and the separation efficiency can reach 99% or more. The method is easy to operate, the obtained material has good stability and super-hydrophilicity, and the oil-water separation effect is remarkable; and meanwhile, due to the fact that the titanium material has the characteristics of being nontoxic, environmentally friendly and the like, the titanium has important significance in the fields of oil-containing sewage treatment, oil recovery and the like.

Description

A kind of preparation method of the super hydrophilic titanium foam for oil-water separation
Technical field
The present invention relates to titanium foam technical field, specifically, relate to a kind of super hydrophilic titanium foam for oil-water separation Preparation method.
Background technology
Titanium foam is a kind of porous metal material with advantages such as nontoxic, environmental friendliness, good biocompatibilities, in recent years Favored by more and more researchers.
The development of material and application, the most inseparable with the technology of preparing of its maturation.The preparation method of titanium foam is closely Year is the most interesting.Its preparation principle is to be mixed, the most under a certain pressure with pore creating material (such as carbamide) by titanium granule (CN103131883A is formed by high-temperature calcination；CN103447533A).By the parameters during regulation, can obtain The titanium foam that porosity differs, thus the space of more more options is provided for its later use.2014, Wang Yao is strange etc. utilized hydrogen Gas auxiliary law, has prepared cheap, the titanium foam (CN104451233A) that porosity is high, has widened titanium foam further Application prospect.
Along with the carrying out of coastal waters exploitation, ocean oil accident happens occasionally；Industry oil-polluted water is also being on the increase simultaneously. This brings huge challenge to oil-water separation.Oil-water separation under weight-driven separates relative to conventional film, have efficiency high, The advantage such as energy-conservation and receive much concern.Porous foam titanium is a kind of well oil-water separation material, but the research of association area is very Few.2015, Li etc. utilized anodic oxidation to be prepared for TiO on titanium foam surface2Nanotube carries out oil-water separation, but the method The Superhydrophilic stability mentioned is the best；What nano tube structure was unfavorable for super hydrophilic interface simultaneously constructs (J. Mater. Chem. A, 2015,3,1279).We, by suitable anodized, form the fluorine oxidation that intrinsic is hydrophilic on titanium foam surface Nitride layer, good stability；And nano surface chamber can significantly improve surface roughness, strengthen super hydrophilicity.This titanium foam has Well oil-water separation.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of super hydrophilic titanium foam for oil-water separation Preparation method.The present invention passes through anodized, the technological means of ultraviolet lighting, prepares good stability, excellent performance Super hydrophilic oil-water separation titanium foam.
To achieve these goals, the present invention adopts the following technical scheme that
The preparation method of a kind of super hydrophilic titanium foam for oil-water separation, comprises the steps:
(1) pre-treatment of material: by titanium foam, successively with acetone, ethanol, deionized water ultrasonic cleaning, remove surface organic with And mineral-type pollutant, then leaching is placed in acetone, stand-by；
(2) anodized: weigh electrolyte, adds water and ethylene glycol configuration electrolyte solution is stand-by；Then with titanium foam it is Anode, titanium foil is negative electrode, under applied voltage effect, carries out anodized, and water bath with thermostatic control temperature is 20-50 DEG C；
(3) ultraviolet lighting processes: titanium foam is dried, is then irradiated with ultraviolet light, to remove the carbon based pollutants on surface Obtain super hydrophilic titanium foam.
As preferably, in above-mentioned preparation method, in step (1), the titanium foam filtering accuracy of employing is below 200 μm, Thickness is 0.1-10mm.
As preferably, in above-mentioned preparation method, electrolyte used in step (2) is villiaumite.
As preferably, in above-mentioned preparation method, the electrolyte weight percent employed in step (2) is 0.1%- 10%。
As preferably, in above-mentioned preparation method, in step (2), two interelectrode distances are 0.1-5cm.
As preferably, in above-mentioned preparation method, using constant voltage dc source in step (2), electric current density controls 1-100m A/cm2。
As preferably, in above-mentioned preparation method, step (2) the Anodic Oxidation process time is 1-12h.
As preferably, in above-mentioned preparation method, described in step (3), ultraviolet light intensity is 1-100 mW/cm2。
As preferably, in above-mentioned preparation method, ultraviolet light described in step (3) is 1-with the distance of titanium foam 20cm。
As preferably, in above-mentioned preparation method, described in step (3), ultraviolet light irradiation time is 1-60min.
Compared with prior art, there is advantages that
The present invention passes through anodic oxidation, the method for ultraviolet lighting, prepares super hydrophilic titanium foam.The titanium foam that this invention obtains, Surface is made up of hydrophilic fluorine titanium oxide, and surface is covered with countless nano-cavity, roughness value R simultaneously, reaches 35.6nm, can To further enhance the hydrophilicity on titanium foam surface.This titanium foam has the superoleophobic characteristic of good super-hydrophilic and underwater, In air, water droplet contact angle is 0 °, and oil contact angle is 160 ° under water, has good oil-water separation.When separation accuracy reaches Below 20 μm, this titanium foam can be also used for emulsion and separates, and separation efficiency can reach more than 99%.The preparation side of the present invention Method, reagent and material are cheap and simple and easy to get, and operational approach is the simplest, and material oil-water separation performance is excellent, and stability is relatively Good.
Accompanying drawing explanation
Fig. 1 is low power and the high power SEM figure of the titanium foam before reaction, and surface is the most smooth；
Fig. 2 is low power and the high power SEM figure of reacted titanium foam, and surface is uniform-distribution with nanoscale cavity；
Fig. 3 be the super hydrophilic titanium foam of preparation air in water contact angle and oily contact angle figure under water, water droplet and oil droplet are 5 μ l；
Fig. 4 is the emulsion separating effect figure of sample, emulsion separate after oil content figure and separation efficiency in water.
Detailed description of the invention
Embodiment 1:
(1) pre-treatment of material: by separation accuracy 20 μm, and the titanium foam of thickness 1mm (purity > 99.7%), successively by acetone, second Alcohol, deionized water at 80KHZ ultrasonic cleaning 10min, remove that surface is organic and mineral-type pollutant, and then leaching is placed in acetone Stand-by.
(2) anodized: weigh 0.3g ammonium fluoride and add 15g water and 84.7g ethylene glycol is configured to percetage by weight The ammonium fluoride electrolyte solution 100g of 0.3% is stand-by.Then with titanium foam as anode, titanium foil is negative electrode, and the two poles of the earth distance is 1.5cm, Under 80V impressed DC voltage effect, carrying out anodized, water bath with thermostatic control temperature is 25 DEG C, reacts 8h, takes out, spends Air-dry after ionized water washing.
(3) ultraviolet lighting processes: by dried titanium foam sample, use 90mW/cm2Uviol lamp, distance sample Sample is irradiated 10 minutes in 20cm position.
Resulting materials, is changed into the surface (such as Fig. 2) being made up of countless nano-cavity by initial flat surface (Fig. 1).From Macroscopically seeing, material is black gray expandable, and in air, water contact angle is 0 °, and oil contact angle is 160 ° (such as Fig. 3) under water.Separated by emulsion Experiment understands: this material has good oil-water separation, and emulsion separation efficiency can reach more than 99%, and for two Toluene, separation efficiency is close to 100%.This material has the strongest prospects for commercial application (such as Fig. 4).
Embodiment 2:
(1) pre-treatment of material: by separation accuracy 20 μm, and the titanium foam of thickness 1mm (purity > 99.7%), successively by acetone, second Alcohol, deionized water at 80KHZ ultrasonic cleaning 10min, remove that surface is organic and mineral-type pollutant, and then leaching is placed in acetone Stand-by.
(2) anodized: weigh 0.4g ammonium fluoride and add 18g water and 81.6g ethylene glycol is configured to percetage by weight The ammonium fluoride electrolyte solution 100g of 0.4% is stand-by.Then with titanium foam as anode, titanium foil is negative electrode, and the two poles of the earth distance is 1.5cm, Under 80V impressed DC voltage effect, carrying out anodized, water bath with thermostatic control temperature is 25 DEG C, reacts 6h, takes out, spends Air-dry after ionized water washing.
(3) ultraviolet lighting processes: by dried titanium foam sample, use 90mW/cm2Uviol lamp, distance sample Sample is irradiated 10 minutes in 20cm position.
Resulting materials, pattern and oil-water separation performance are all basically identical with embodiment 1.

Claims (10)

1. the preparation method of a super hydrophilic titanium foam, it is characterised in that comprise the steps:
(1) pre-treatment of material: by titanium foam, successively with acetone, ethanol, deionized water ultrasonic cleaning, remove surface organic with And mineral-type pollutant, then leaching is placed in acetone, stand-by；
(2) anodized: weigh electrolyte, adds water and ethylene glycol configuration electrolyte solution is stand-by；Then with titanium foam it is Anode, titanium foil is negative electrode, under applied voltage effect, carries out anodized, and water bath with thermostatic control temperature is 20-50 DEG C；
(3) ultraviolet lighting processes: titanium foam is dried, is then irradiated with ultraviolet light, to remove the carbon based pollutants on surface Obtain super hydrophilic titanium foam.
2. preparation method as claimed in claim 1, it is characterised in that the titanium foam filtering accuracy used in step (1) is at 200 μ Below m, thickness is 0.1-10mm.
3. preparation method as claimed in claim 1, it is characterised in that electrolyte used in step (2) is villiaumite.
4. preparation method as claimed in claim 1, it is characterised in that the electrolyte weight percent employed in step (2) is 0.1%-10%。
5. preparation method as claimed in claim 1, it is characterised in that in step (2), two interelectrode distances are 0.1-5cm.
6. preparation method as claimed in claim 1, it is characterised in that use constant voltage dc source, electric current density in step (2) Control at 1-100m A/cm2。
7. preparation method as claimed in claim 1, it is characterised in that step (2) the Anodic Oxidation process time is 1-12h.
8. preparation method as claimed in claim 1, it is characterised in that described in step (3), ultraviolet light intensity is 1-100 mW/cm2。
9. preparation method as claimed in claim 1, it is characterised in that described in step (3), ultraviolet light with the distance of titanium foam is 1-20cm。
10. preparation method as claimed in claim 1, it is characterised in that described in step (3), ultraviolet light irradiation time is 1- 60min。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108179454A (en) * 2017-12-29 2018-06-19 重庆大学 A kind of preparation method of the super infiltration titanium foam of water-oil separating
CN108516605A (en) * 2018-05-11 2018-09-11 湖南国昶能源科技有限公司 A kind of Self-priming oil-water separator
CN110038569A (en) * 2019-05-22 2019-07-23 安徽理工大学 A kind of Janus Cu (OH)2@Cu2O/Cu net and preparation method thereof, application

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CN101302630A (en) * 2008-01-17 2008-11-12 上海交通大学 Method for preparing metal by means of solid oxide electrolytic cell
CN103173835A (en) * 2011-12-22 2013-06-26 中国科学院大连化学物理研究所 Treating method of metallic titanium material
CN103949167A (en) * 2014-04-21 2014-07-30 北京航空航天大学 Preparation method of micro-nano oil-water separation membrane with self-cleaning and underwater ultra-oleophobic properties

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CN101302630A (en) * 2008-01-17 2008-11-12 上海交通大学 Method for preparing metal by means of solid oxide electrolytic cell
CN103173835A (en) * 2011-12-22 2013-06-26 中国科学院大连化学物理研究所 Treating method of metallic titanium material
CN103949167A (en) * 2014-04-21 2014-07-30 北京航空航天大学 Preparation method of micro-nano oil-water separation membrane with self-cleaning and underwater ultra-oleophobic properties

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108179454A (en) * 2017-12-29 2018-06-19 重庆大学 A kind of preparation method of the super infiltration titanium foam of water-oil separating
CN108516605A (en) * 2018-05-11 2018-09-11 湖南国昶能源科技有限公司 A kind of Self-priming oil-water separator
CN110038569A (en) * 2019-05-22 2019-07-23 安徽理工大学 A kind of Janus Cu (OH)2@Cu2O/Cu net and preparation method thereof, application
CN110038569B (en) * 2019-05-22 2021-11-19 安徽理工大学 Janus Cu (OH)2@Cu2O/Cu net and preparation method and application thereof

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