CN103695955B - Method for preparing TiO2 photocatalyst by using titanium tanning waste water - Google Patents
Method for preparing TiO2 photocatalyst by using titanium tanning waste water Download PDFInfo
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- CN103695955B CN103695955B CN201310711800.XA CN201310711800A CN103695955B CN 103695955 B CN103695955 B CN 103695955B CN 201310711800 A CN201310711800 A CN 201310711800A CN 103695955 B CN103695955 B CN 103695955B
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Abstract
The invention discloses a method for preparing a TiO2 photocatalyst by using titanium tanning waste water. The method comprises the following preparation steps of: selecting a precious metal gold sheet or platinum sheet as an anode and a coating-free 301 stainless steel sheet or aluminum, with the same area as that of the anode, as a cathode; deoiling the anode by using a detergent, acetone and ethanol in sequence, performing ultrasound on the anode for 15min with acetone, absolute ethanol and deionized water respectively, and drying the anode for later use; polishing a polar plate of the cathode by using No. 4 abrasive paper for metallograph, washing the polar plate of the cathode with a detergent, acetone and absolute ethanol in sequence for deoiling, putting the cathode in a mixture solution of hydrochloric acid and ethanol with the volume ratio being 1:1 for corroding for 1-5min, performing ultrasound for 15min by using acetone, absolute ethanol and deionized water respectively, and drying the cathode for later use. According to the method disclosed by the invention, the TiO2 anatase type photocatalyst designed and prepared by using the titanium tanning waste water from tanning processing has good light and heat stability, high activity and reusability, and has a good effect on degrading refractory dyeing wastewater.
Description
Technical field
The present invention relates to a kind for the treatment of of wastes with processes of wastes against one another, prepares the pure anatase of high activity using the titanium tannage waste water in electrolysis process hides tanning
Type TiO2Method.
Background technology
Process hides tannery is one of topmost process in leather industry, and global more than 90% tanning production will be carried out
Tannery, the average annual chrome tanning agent demand in the world cause pollution of chromium in leather waste water up to 400,000 t.Current part vamp, clothes
In dress, sofa and the production of the light leather needed for leather goods, part combines tanning using zirconium, titanium tannage system or many metals, wherein titanium tannage agent because
Combination property is only second to chrome tanning agent so as to which product quantity is in growth trend year by year.But, tan is although made using new titanium tannage waste water
Chromium concn and unit product chromium consumption in waste water processed is greatly lowered, but brings new titanium ion to pollute, especially greatly
Tanning waste water in part is highly acid, makes titanium and exists with the complex form of free ion or titanium, to wastewater biochemical system in it is micro-
Biological to have genotoxic potential, urgent need is recycled.
TiO2As a kind of stable performance, the excellent photocatalyst of cheap, catalysis activity high (comparing with rutile),
Splendid diving is shown at aspects such as degradation of dye waste water, agricultural chemicals waste water, surfactant, halo waste water, inorganic wastewaters
Power, in the world by TiO2Commercialization, is applied to the aspects such as ceramic purifying, coating, sterilization.Being commercially as photocatalyst makes
TiO2Relate generally to two kinds of crystal formations：Detitanium-ore-type and rutile-type, Detitanium-ore-type TiO2Catalytic performance be significantly larger than golden red
Stone-type.
Current Detitanium-ore-type TiO2The preparation method of comparative maturity is mainly：Sol-gal process and sedimentation, but all exist
Response time is long, and crystal form is difficult to the shortcomings of controlling.Wherein sol-gal process is mainly for the preparation of TiO2Powder, and sedimentation is main
For preparing TiO2Thin film.Powder-type TiO2With larger specific surface area, there is higher activity, together in photocatalytic process
When, titanium tannage waste water itself contains substantial amounts of titanium tannage agent, and its main component is titanyl sulfate double salt, and in water, easily hydrolysis becomes titanium
Hydroxyl compound, the latter can form titanium oxide in electrolytic process.
Combined with electrochemical method of the present invention and powder-type TiO2Advantage, according to the treatment of wastes with processes of wastes against one another thought, with leather making process
Based on the composition of titanium tannage waste water, a kind of electrolytic preparation Detitanium-ore-type TiO is invented2Method, and by the catalyst for preparing
Preferable result is obtained for photocatalytic degradation of dye waste water.
The content of the invention
It is an object of the present invention to provide a kind of prepare TiO using titanium tannage waste water2The method of photocatalyst, while utilizing
The wet-white leather titanium tannage produced in leather making process or retanning waste water, prepare Detitanium-ore-type TiO2While photocatalyst, which can be utilized
Degraded leather dye waste water, realizes recycling economy.
To solve above-mentioned technical problem, embodiments of the invention provide a kind of using titanium tannage waste water preparation TiO2Photocatalyst
Method, the preparation process is as follows：
((1) chooses noble metal gold plaque or platinized platinum is anode, and uncoated 301 stainless steel substrates of homalographic or aluminium flake are used as the moon
Pole；
(2) successively with detergent, acetone and ethanol to anode oil removing, and distinguished with acetone, dehydrated alcohol and deionized water
Ultrasound 15 minutes, is dried, standby；
(3) 4 are used#Abrasive paper for metallograph is polished to cathode plate, successively with detergent, acetone, absolute ethanol washing negative electrode
Pole plate oil removing, places into hydrochloric acid and ethanol volume ratio to corrode 1～5 minute in 1: 1 mixed solution, with acetone, dehydrated alcohol
It is ultrasonic 15 minutes respectively with deionized water, it is dried, it is standby；
(4) minus plate obtained by the positive plate obtained by step (2) and step (3) is placed on existing wet-white leather titanium tannage to give up
Water, or retanning waste water, used as in the aseptate electrolysis bath of electrolyte, the two poles of the earth are at a distance of 40mm, 4～12V of control voltage, electrolysis bath
At 20～30 DEG C, electrolysis time is 10～30min to temperature control, obtains white precipitate；
(5) white precipitate obtained by step (4) is centrifuged, 3～5 after bake of deionized water cyclic washing
It is dry, after being ground with agate mortar, it is placed in crucible, calcines in muffle furnace, obtain flaxen powder.
The main component of the electrolyte is：Tannin：1～5%, formic acid：0.1～2%, titanium tannage agent：10～60%, nitre
Sour potassium：1～6%, acrylic acid：0.1～2%, dicyandiamide：1～5%, fatting agent：0.1～1%.
The pH value of the titanium tannage waste water is 2.5～3.8.
The titanium concentration of the titanium tannage waste water is 0.5～250mg/L.
The titanium tannage waste water need to remove therein suspension particulate matter to process through below 0.01mm screen filtrations.
Calcination time in the step (5)：30min～4h, calcining heat is：200～450 DEG C, the muffle furnace is railway carriage or compartment
Formula muffle furnace.
The beneficial effects of the present invention is the TiO for preparing is designed using titanium tannage waste water2Have for pure Detitanium-ore-type photocatalyst
There is light and heat stability, activity is high, has good degradation effect to the waste water from dyestuff of difficult degradation.
Description of the drawings
Fig. 1 is pure Detitanium-ore-type TiO prepared by sol-gal process2With the XRD ratios of the titanium dioxide optical catalyst of the present invention
Relatively scheme.
Fig. 2 is the pure Detitanium-ore-type TiO prepared by sol-gal process under Metal halogen lamp irradiation2With the titanium dioxide of the present invention
Photocatalyst for degrading methyl orange dye waste water, solution percent of decolourization change over curve.
Fig. 3 is the pure Detitanium-ore-type TiO prepared by sol-gal process under Metal halogen lamp irradiation2With the titanium dioxide of the present invention
Photocatalyst for degrading methyl orange dye waste water, solution C OD degradation rate change over curve.
Specific embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
Below by the pure Detitanium-ore-type TiO that specific embodiment is prepared to the present invention2It is described further, its purpose only exists
In being best understood from present disclosure rather than limit the scope of the invention.
Embodiment 1
In aseptate electrolysis bath, using DC source, control voltage is：10V.Electrolyzer temperature is 25 DEG C, area phase
Same platinum sheet and uncoated aluminium sheet are respectively anode and negative electrode, are electrolysis from the wet-white leather titanium tannage waste water of certain tanning production factory
Electrolyte is carried out filtration treatment before electrolysis by liquid, and the pH of electrolyte is 3.6～3.8, and anode platinized platinum uses detergent, acetone successively
With dehydrated alcohol oil removing, and with acetone, dehydrated alcohol and deionized water respectively ultrasound 15 minutes, be dried, it is standby；Cathode aluminum plate
Jing 4#Detergent, acetone and dehydrated alcohol oil removing are used after abrasive paper for metallograph polishing and successively, it is 1 to place into hydrochloric acid and ethanol volume ratio
: corrode 1～5 minute in 1 mixed solution, and it is ultrasonic 15 minutes respectively with acetone, dehydrated alcohol and deionized water, it is dried standby
With.Electrolysis 30min prepares TiO2, the white precipitate of bottom of electrolytic tank is collected after the completion of electrolysis, after being dried in vacuum drying oven
Collect and powder is ground in agate mortar, 400 DEG C of calcinings in muffle furnace are obtained corresponding Detitanium-ore-type in 60 minutes
TiO2Photocatalyst.
Fig. 1 provides the pure Detitanium-ore-type TiO of sol-gal process preparation2Urge with the pure anatase titanium dioxide light of the present invention
The XRD of agent compares.(a) in Fig. 1 is pure Detitanium-ore-type TiO prepared by sol-gal process2XRD, (b) be electrolysis of the present invention
Pure anatase titanium dioxide catalyst XRD (before calcining).C () is the pure Detitanium-ore-type titanium dioxide after final calcining of the invention
Titanium catalyst XRD.From the comparison of Fig. 1, the titanium dioxide optical catalyst prepared before and after clearly showing present invention calcining shows sharp titanium
The characteristic peak of ore deposit.
By this experiment gained pure Detitanium-ore-type TiO2TiO is prepared with sol-gal process2Contrast, in 400W gold-halogen lamp light sources
Under, with methyl orange dye waste water as target solution, target solution is positioned in 8L cylindrical quartz reactors, by light source Jing cold-traps
Protection insertion reaction device center, the change of methyl orange solution percent of decolourization after last recording light source pre-irradiation, their comparison diagram are shown in
Fig. 2, and according to the COD value change calculations degraded percentage rate of waste water from dyestuff before and after degraded, their comparison diagram is shown in Fig. 3.
Fig. 2 is that this experiment prepares pure Detitanium-ore-type TiO with 200mg2Photocatalyst or 200mg sol-gal processes prepare pure
Detitanium-ore-type TiO2Under 400W gold-halogen lamp light sources, the methyl orange dye waste water of the 2L200mg/L that degrades, solution decolourize photocatalyst
Rate changes over curve, wherein,
A () curve is the pure Detitanium-ore-type TiO of this experiment gained2In the presence of；
B () curve prepares pure Detitanium-ore-type TiO for sol-gal process2In the presence of；
Fig. 3 is that this experiment prepares pure Detitanium-ore-type TiO with 200mg2Photocatalyst or 200mg sol-gal processes prepare pure
Detitanium-ore-type TiO2Photocatalyst under 400W gold-halogen lamp light sources, degrade 2L200mg/L methyl orange dye waste water, solution C OD
Degradation rate changes over curve, wherein,
A () curve is the pure Detitanium-ore-type TiO of this experiment gained2In the presence of；
B () curve prepares pure Detitanium-ore-type TiO for sol-gal process2In the presence of；
As shown in Figures 2 and 3, under the irradiation of 400W Metal halogen lamps, the pure Detitanium-ore-type TiO of this experiment gained2And collosol and gel
Detitanium-ore-type TiO prepared by method2All there are good decolorizing effect and degradation effect to methyl orange dye waste water, degrade 150min
Afterwards, methyl orange almost more than 90% decolouring；Meanwhile, can be seen that from COD degradation rate, the TiO prepared with the present invention2Almost can be complete
Break the molecular structure of methyl orange, and TiO prepared by sol-gel process2Its molecular structure can not be made to rupture completely, it is seen that this
Pure Detitanium-ore-type TiO in bright2Degradation effect be far superior to sol-gal process prepare TiO2。
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, some improvements and modifications can also be made, these improvements and modifications
Should be regarded as protection scope of the present invention.
Claims (1)
1. it is a kind of to prepare TiO using titanium tannage waste water2The method of photocatalyst, it is characterised in that the preparation process is as follows：
(1) it is anode to choose noble metal gold plaque or platinized platinum, and uncoated 301 stainless steel substrates of homalographic or aluminium flake are used as negative electrode；
(2) it is successively with detergent, acetone and ethanol to anode oil removing and ultrasonic respectively with acetone, dehydrated alcohol and deionized water
15 minutes, it is dried, it is standby；
(3) 4 are used#Abrasive paper for metallograph is polished to cathode plate, is removed with detergent, acetone, absolute ethanol washing cathode plate successively
Oil, places into hydrochloric acid and ethanol volume ratio to corrode 1～5 minute in 1: 1 mixed solution, with acetone, dehydrated alcohol and go from
Sub- water is ultrasonic 15 minutes respectively, is dried, standby；
(4) minus plate obtained by the positive plate obtained by step (2) and step (3) is placed on into existing wet-white leather titanium tannage waste water, or
, used as in the aseptate electrolysis bath of electrolyte, the two poles of the earth are at a distance of 40mm, 4～12V of control voltage, electrolyzer temperature control for retanning waste water
At 20～30 DEG C, electrolysis time is 10～30min to system, obtains white precipitate；
(5) white precipitate obtained by step (4) is centrifuged, 3～5 post-dryings of deionized water cyclic washing, is used
After agate mortar grinding, it is placed in crucible, calcines in muffle furnace, obtain flaxen powder；
The main component of the electrolyte is：Tannin：1～5%, formic acid：0.1～2%, titanium tannage agent：10～60%, potassium nitrate：1
～6%, acrylic acid：0.1～2%, dicyandiamide：1～5%, fatting agent：0.1～1%；
The pH value of the titanium tannage waste water is 2.5～3.8；
The titanium concentration of the titanium tannage waste water is 0.5～250mg/L；
The titanium tannage waste water need to remove therein suspension particulate matter to process through below 0.01mm screen filtrations；
Calcination time in the step (5)：30min～4h, calcining heat is：200～450 DEG C, the muffle furnace is van-type horse
Fluorine stove.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314975A (en) * | 1979-11-11 | 1982-02-09 | Motov David L | Method for preparing titanium tanning agent |
| CN101358252A (en) * | 2008-09-28 | 2009-02-04 | 四川大学 | Tanning method of nano SiO2 or TiO2 tanning agents |
| CN102605382A (en) * | 2011-12-19 | 2012-07-25 | 浙江师范大学 | Method for preparing high-purity nanometer titanium dioxide by electrolyzing titanium trichloride |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61133300A (en) * | 1984-12-03 | 1986-06-20 | ロリス・グイデイ | Leather tanning method |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4314975A (en) * | 1979-11-11 | 1982-02-09 | Motov David L | Method for preparing titanium tanning agent |
| CN101358252A (en) * | 2008-09-28 | 2009-02-04 | 四川大学 | Tanning method of nano SiO2 or TiO2 tanning agents |
| CN102605382A (en) * | 2011-12-19 | 2012-07-25 | 浙江师范大学 | Method for preparing high-purity nanometer titanium dioxide by electrolyzing titanium trichloride |
Non-Patent Citations (3)
| Title |
|---|
| Application of Doehlert matrix to the study of electrochemical oxidation of Cr(III) to Cr(VI) in order to recover chromium from wastewater tanning baths;A.Ouejhani et al;《Journal of Hazardous Materials》;20080119(第157期);第423-431页 * |
| 电化学方法制备纳米金属氧化物的研究;景介辉;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》;20051015;第16页，第17页第1.2节，第19页第1段，第25页倒数第1段 * |
| 鞣革用钛配合物的性能及其应用前景;李闻欣 等;《中国皮革》;20061203;第35卷(第23期);第39页第1段 * |
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