CN103803682A - Method for preparing iron composite filler loaded with carbon nanotube - Google Patents
Method for preparing iron composite filler loaded with carbon nanotube Download PDFInfo
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- CN103803682A CN103803682A CN201410049887.3A CN201410049887A CN103803682A CN 103803682 A CN103803682 A CN 103803682A CN 201410049887 A CN201410049887 A CN 201410049887A CN 103803682 A CN103803682 A CN 103803682A
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Abstract
The invention discloses a method for preparing iron composite filler loaded with a carbon nanotube. With waste scrap iron and a multi-walled carbon nanotube as raw materials, the method comprises the steps of putting sheet iron and the carbon nanotube into an isopropyl alcohol solution containing magnesium chloride with the concentration of 0.003mol/L; along with ultrasonic treatment, performing electrophoretic deposition for 1-3 hours under 160V voltage and 1mA current so that the carbon nanotube is adhered to the sheet iron; drying the prepared composite filler for 2-3 hours at a temperature of 40 DEG C; then roasting in an argon flow at a temperature of 600 DEG C to obtain the set composite filler finally. By adopting the method disclosed by the invention, the obtained filler has a relatively large specific surface area and a high mass transfer rate, and the surface passivation and hardening of the filler can be effectively prevented; the biodegradability of the printing and dyeing wastewater can be improved in short time, and the CODcr and chroma of the wastewater are reduced; the process is simple and easy to popularize and facilitates industrial production.
Description
Technical field
The invention belongs to iron-carbon micro-electrolysis technical field of sewage, especially relate to a kind of method of the Iron-complex-filling of preparing load carbon nanotube.
Background technology
Textile industry is one of department that China's discharge amount of industrial wastewater is larger, according to incompletely statistics, annual waste discharge amount reaches more than 900,000,000 ton, occupy the 6th of China's discharged volume of industrial waste water, wherein dyeing waste water quantity discharged accounts for 80% of textile waste quantity discharged, is one of industry that China's waste discharge and amount of pollutant are larger.Dyeing waste water has the features such as the water yield is large, organic pollutant content is high, colourity dark, alkalescence is large, change of water quality is large, biodegradability is poor, and conventional physical chemistry, biological treatment is difficult to meet technology and the requirement of Economic development to water quality treatment.Iron filings are a kind of solid wastes in machine works's production process, and discarded iron filings are stacked not only land occupation for a long time in a large number, and can influence ecological environment.At present, the recycling of waste iron filing is also widely studied.
Micro-electrolysis method is based on electrochemical principle of oxidation and reduction, the chemical treatment technology of the galvanic cell consisting of reaction medium to waste water.Conventional iron-carbon micro-electrolysis reaction is easily carried out under acidic conditions, and in acidic solution, the nascent state that cathodic reaction generates, has very high chemically reactive, can destroy organic color development or auxochrome group in dyeing waste water, reaches the object of waste water decoloring.The Fe that anodic reaction is newly-generated
2+and the Fe that further oxidation generates
3+, the Fe (OH) generating under alkaline condition
2and Fe (OH)
3there is stronger absorption and sedimentation capacity, thereby dyeing waste water is purified.That its advantage is is with low cost, technique simple, have wide range of applications, but traditional micro-electrolysis process is after equipment operation for some time, can there is passivation, harden due to the precipitation of the oxide compound of iron and oxyhydroxide in the iron filings in filler, reduce speed of reaction, cause sewage in filler, to produce channel, affect effluent quality, make micro-electrolysis reactor want frequent back flushing and replacement; Meanwhile, in order to strengthen the effect of traditional Fe-C Micro Electrolysis Method, usually adopt assisting ultrasonic processing to carry out the mass transfer between intensifier electrode, or add Fenton reagent, act synergistically with iron-carbon micro-electrolysis.These measures have increased the real cost of sewage disposal, are the major reasons that restriction this method is promoted.
Many investigators propose respectively with alternative iron carbon materials such as simple iron filings, iron-copper combined stuffing, gac-ferrous manganese ore combined stuffings, but because the impure amount of simple iron filings is limited, micro-electrolytic action relatively a little less than, and take reduction reaction as main, application is restricted.Use copper as negative electrode, can improve reduction reaction rate, but iron-copper combined stuffing cost is high.Carbon nanotube, because it has unique structure and excellent electricity, mechanical property, is widely used in the numerous areas such as electrode materials, support of the catalyst and matrix material, has broad application prospects in industry and high-tech area.Prevention and solve filling surface passivation, the filler problem that hardens, improves micro-electrolysis reaction speed, and reducing costs is the key point of micro electrolysis tech development from now on.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of method of the Iron-complex-filling of preparing load carbon nanotube, make full use of discarded this waste resource of iron filings and multi-walled carbon nano-tubes, can be widely used in processing and the pre-treatment of dyeing waste water.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
A method of preparing the Iron-complex-filling of load carbon nanotube, comprises the following steps:
1) multi-walled carbon nano-tubes is heated to 30-60min at the temperature of 350 ℃, and with hydrochloric acid cleaning, remove surface impurity;
2) carbon nanotube obtaining in step 1) is immersed in volume ratio 1 concentrated nitric acid of ﹕ 3 and the mixed solution of the vitriol oil, then mixture is fully stirred to 15-20h;
3) by step 2) in mixed solution filter, distilled water cleans, dry at 150 ℃, utilize agate mortar to be stored in dry vial after grinding;
4) iron filings that sieve is got particle diameter 1 ~ 2mm are first used 10% Na
2cO
3solution soaking 12h to be to remove surface and oil contaminant, then activates 30min with 2% dilute sulphuric acid, cleans up subsequently and dry with tap water;
5) utilize powder pressure machine under the pressure of 200kN, pressing step 4) in iron filings after treatment, make the iron plate of sizing;
6) iron plate of making in step 5) and the carbon nanotube of handling well are put into the aqueous isopropanol that is dissolved with 0.003mol/L magnesium chloride, follow supersound process, at 160V voltage, under 1mA electric current, carry out electrophoretic deposition 1-3h;
7) by the Iron-complex-filling of the load carbon nanotube making in step 6) dry 2-3h at the temperature of 40 ℃, then by it as in argon gas stream, in 600 ℃ of roasting temperature 3-6h, finally obtain the compounded mix of sizing.
The Iron-complex-filling of the prepared load carbon nanotube of aforesaid method.
The application of the Iron-complex-filling of described load carbon nanotube in treatment of dyeing wastewater.
Beneficial effect: compared with prior art, the present invention has the following advantages:
1) utilize discarded iron filings to replace traditional Zero-valent Iron as electrode materials, prepare microelectrode material and carry out treatment of dyeing and printing, reached the object of " treatment of wastes with processes of wastes against one another ", economic environmental protection.
2) because the caliber of multi-walled carbon nano-tubes is no more than 100nm, and then can be in the numerous microcosmic iron carbon galvanic cell unit of quantity of formation, waste iron filing surface, specific surface area is large, carbon nanotube has unique structure and excellent electricity, mechanical property because of it, and the iron carbon dioxide process carbon electrode that is applied to the more traditional macroscopic aspect of electrode materials has obvious quantity and transfer efficiency advantage.
3) preparation cost of the present invention is lower, and working service is simple, and technological operation is simple, can be widely used in processing and the pre-treatment of dyeing waste water, has good application prospect.
Accompanying drawing explanation
Fig. 1 is the cylindricality reactor of the Iron-complex-filling of filling load carbon nanotube.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
The iron filings that following examples are used are taken from Nanjing machine works.Multi-walled carbon nano-tubes (caliber 50-90nm, length 5-15 μ m, purity >98%) is purchased from Shenzhen nanosecond science and technology company.
Embodiment 1
In order to remove the organic and inorganic impurity on multi-walled carbon nano-tubes, present method first to multi-walled carbon nano-tubes heat, the pre-treatment such as pickling, oxidation.Multi-walled carbon nano-tubes need be heated to 30-60 minute at the temperature of 350 ℃, and use hydrochloric acid cleaning.Then immersed in 69% concentrated nitric acid of volume ratio 1 ﹕ 3 and the mixed solution of 98% vitriol oil, then mixture is fully stirred at least 15h of 19h(), distilled water filters, is dried (150 ℃), grinds after (agate mortar grinds, particle diameter≤80nm), is stored in dry vial.To screen (particle diameter 1 ~ 2mm), clean (10% Na2CO3 solution soaking 12h, remove surface and oil contaminant,), iron filings after activation (2% dilute sulphuric acid activation 30min) utilize powder pressure machine to suppress under the pressure of 200kN, isolated air heating, obtain iron plate (4cm × 4cm × 2mm) after quenching.The multi-walled carbon nano-tubes of handling well, iron plate are added and have 0.003mol/L magnesium chloride in electrolytical aqueous isopropanol, at 160V voltage, under 1mA electric current, be accompanied by supersound process (the KQ-600 type ultrasonic generator (600W) of 60kHz, at room temperature supersound process), realize carbon nanotube adhering on iron plate by carrying out the electrophoretic deposition of 90min.Have the iron plate of carbon nanotube to be placed in dry 2-3h at the temperature of 40 ℃ by producing load after electrophoretic deposition, and then by it as in argon gas stream, in 600 ℃ of roasting temperature 4h.Obtain the Iron-complex-filling for the load carbon nanotube for the treatment of of dyeing wastewater.
Embodiment 2
The Iron-complex-filling of the load carbon nanotube that embodiment 1 is made, fill in the reactor shown in Fig. 1, in figure, 1 is reaction unit water outlet, and 2,3 are thief hole, and 4 is reaction unit dividing plate (this device adopts wire netting), 5 for connecing air scoop, 6 is water-in, and 7 is appliance stand, and 8 is packing area.Filler loading height is 30cm, and tap density is 800kg/m
3, carry out application test.
Take from the dyeing waste water of Suzhou dye chemical industry factory, its effluent quality situation is: COD
crfor 697.56mg/L, BOD
5for 138.2mg/L, pH are 9.7,480 times of colourities, first the pH of waste water is modulated to 4 left and right, then with peristaltic pump, the waste water in water tank is entered to reactor, hydraulic detention time is 2h, water outlet COD after micro-electrolysis
crfor 60.3mg/L, BOD
5for 19.9mg/L, colourity is 30 times, COD
cr, BOD
5, colourity clearance be respectively 91.4%, 85.6%, 93.8%, B/C has risen to 0.33 from 0.198, has improved the biodegradability of waste water; Through the continuous experiment of month, it is good that filler form keeps, the phenomenon such as do not occur passivation, harden.
Embodiment 3
Method and apparatus is all with embodiment 2.
Waste water is taken from the A/O secondary effluent of Anhui printing and dyeing mill, and its effluent quality situation is: COD
crfor 450mg/L, BOD
5for 110mg/L, pH are 2.5,200 times of colourities, first the pH of waste water is modulated to 3 left and right, then with peristaltic pump, the waste water in water tank is entered to reactor, hydraulic detention time is 1.5h, water outlet COD after micro-electrolysis
crfor 54mg/L, BOD
5for 21mg/L, colourity is 2 times, COD
cr, BOD
5, colourity clearance be respectively 88%, 80.9%, 94%, B/C has risen to 0.389 from 0.244.Through the continuous experiment of 45 days, it is good that filler form keeps, the phenomenon such as do not occur passivation, harden.
Claims (3)
1. a method of preparing the Iron-complex-filling of load carbon nanotube, is characterized in that, comprises the following steps:
1) multi-walled carbon nano-tubes is heated to 30-60min at the temperature of 350 ℃, and with hydrochloric acid cleaning, remove surface impurity;
2) carbon nanotube obtaining in step 1) is immersed in volume ratio 1 concentrated nitric acid of ﹕ 3 and the mixed solution of the vitriol oil, then mixture is fully stirred to 15-20h;
3) by step 2) in mixed solution filter, distilled water cleans, dry, grind, be stored in dry vial;
4) iron filings that sieve is got particle diameter 1 ~ 2mm are first used 10% Na
2cO
3solution soaking 12h to be to remove surface and oil contaminant, then activates 30min with 2% dilute sulphuric acid, cleans up subsequently and dry with tap water;
5) utilize powder pressure machine under the pressure of 200kN, pressing step 4) in iron filings after treatment, make the iron plate of sizing;
6) iron plate of making in step 5) and the carbon nanotube of handling well are put into the aqueous isopropanol that is dissolved with 0.003mol/L magnesium chloride, follow supersound process, at 160V voltage, under 1mA electric current, carry out electrophoretic deposition 1-3h;
7) by the Iron-complex-filling of the load carbon nanotube making in step 6) dry 2-3h at the temperature of 40 ℃, then by it as in argon gas stream, in 600 ℃ of roasting temperature 3-6h, finally obtain the compounded mix of sizing.
2. the Iron-complex-filling of the prepared load carbon nanotube of the method for the Iron-complex-filling of preparation load carbon nanotube claimed in claim 1.
3. the application of the Iron-complex-filling of load carbon nanotube claimed in claim 2 in treatment of dyeing wastewater.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801274A (en) * | 2015-04-23 | 2015-07-29 | 河海大学 | Antibiotic adsorption bag and application of antibiotic adsorption bag in in-situ repair of aquatic sediment polluted by antibiotic |
| CN106076397A (en) * | 2016-06-06 | 2016-11-09 | 同济大学 | A kind of preparation method of Zero-valent Iron carbon nano-tube modification Zeolite composite materials |
| CN108640296A (en) * | 2018-06-08 | 2018-10-12 | 盛勇 | A kind of composite biological material and preparation method thereof of iron content carbon nanotube |
| CN109590460A (en) * | 2018-12-17 | 2019-04-09 | 浙江工业大学 | A kind of soft-magnetic composite material and preparation method thereof |
| CN110544771A (en) * | 2019-08-23 | 2019-12-06 | 暨南大学 | Low-voltage high-loading self-supporting potassium ion battery cathode and preparation and application thereof |
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| CN101856626A (en) * | 2010-05-07 | 2010-10-13 | 上海电力学院 | Preparation method of catalyst of carbon multi-wall nano tube loaded metal platinum nano particle with surface nitrile-group modification |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
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2014
- 2014-02-13 CN CN201410049887.3A patent/CN103803682A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856626A (en) * | 2010-05-07 | 2010-10-13 | 上海电力学院 | Preparation method of catalyst of carbon multi-wall nano tube loaded metal platinum nano particle with surface nitrile-group modification |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
Non-Patent Citations (1)
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| 周亮: "活性炭及改性碳纳米管催化臭氧降解亚甲基蓝", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 8, 15 August 2013 (2013-08-15) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801274A (en) * | 2015-04-23 | 2015-07-29 | 河海大学 | Antibiotic adsorption bag and application of antibiotic adsorption bag in in-situ repair of aquatic sediment polluted by antibiotic |
| CN106076397A (en) * | 2016-06-06 | 2016-11-09 | 同济大学 | A kind of preparation method of Zero-valent Iron carbon nano-tube modification Zeolite composite materials |
| CN108640296A (en) * | 2018-06-08 | 2018-10-12 | 盛勇 | A kind of composite biological material and preparation method thereof of iron content carbon nanotube |
| CN108640296B (en) * | 2018-06-08 | 2021-04-06 | 盛勇 | Composite biological material containing iron carbon nano-tube and preparation method thereof |
| CN109590460A (en) * | 2018-12-17 | 2019-04-09 | 浙江工业大学 | A kind of soft-magnetic composite material and preparation method thereof |
| CN110544771A (en) * | 2019-08-23 | 2019-12-06 | 暨南大学 | Low-voltage high-loading self-supporting potassium ion battery cathode and preparation and application thereof |
| CN110544771B (en) * | 2019-08-23 | 2021-02-05 | 暨南大学 | Low-voltage high-loading self-supporting potassium ion battery cathode and preparation and application thereof |
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Application publication date: 20140521 |