CN101259413A - Method for preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method - Google Patents
Method for preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method Download PDFInfo
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- CN101259413A CN101259413A CNA2008101033488A CN200810103348A CN101259413A CN 101259413 A CN101259413 A CN 101259413A CN A2008101033488 A CNA2008101033488 A CN A2008101033488A CN 200810103348 A CN200810103348 A CN 200810103348A CN 101259413 A CN101259413 A CN 101259413A
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- ilmenite
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Abstract
A method for preparing photocatalysis material by taking ilmenite concentrates as the raw materials belongs to the field of functional materials. The invention is characterized in that firstly concentrated hydrochloric acid is used for decomposing the ilmenite, thus leading the ferrum and titanium elements to enter a solution; then a chemical precipitation method is adopted for purifying the ferrum and titanium elements; the zinc element can be adulterated according to demand; the metal multiple oxide photocatalysis material is prepared by the sol-gel combustion synthesizing technique through the complexation of citric acid. The invention comprehensively utilizes two components of ferrum and titanium in the ilmenite, thus avoiding the recycling working procedure of the by-product containing ferrum. The method is a new technology for preparing the novel photocatalysis material with low cost. The prepared photocatalysis material has the advantages of thin particles, high photocatalysis activity and higher light absorption in both ultraviolet zone and visible light zone, and can be applied to the solar energy utilizing field like photocatalysis and photoelectric conversion, etc., and has excellent application prospects.
Description
Technical field
The invention belongs to field of functional materials, particularly providing a kind of is that raw material adopts wet chemistry method to prepare the method for catalysis material with the ilmenite concentrate.
Background technology
By photochemical catalytic oxidation reduction effect degraded noxious pollutant, non-secondary pollution is the environmental type catalysis technique with exploitation future.Polytype many composite oxide of metal have good redox property, and show greater activity in chemical reaction, wherein perovskite ABO
3Composite oxides, perovskite-like A
2BO
4Composite oxides and spinelle AB
2O
4Composite oxides are novel semi-conductor catalysis materials of three kinds of different structures, have visible light utilization rate height, characteristics that photocatalysis efficiency is high.Iron titanium oxide and zinc-iron oxides more and more are subjected to people's attention at electrode, gas sensor, magnetic material, catalyst especially for the application in fields such as catalytic decomposition carbon dioxide, have wide potential application foreground.Zinc-iron oxides is as the existing report of the research of novel semi-conductor catalysis material, and iron titanium oxide does not appear in the newspapers both at home and abroad as yet as the research of conductor photocatalysis material.
The reserves of ilmenite are extremely abundant in the world, and the reserves of China's titanium iron ore are at the forefront in the world.Ilmenite can be used to produce synthetic rutile, high titanium slag, titanium sponge, titanium alloy, titanium dioxide etc., but the ferro element in the ilmenite all is used as impurity and removes in process of production, form a large amount of iron bearing by-products, and the technology more complicated, utilize process to have many difficulties.At present in the ilmenite comprehensive utilization process otherwise energy consumption too high, or the comprehensive utilization degree of iron is low.The present invention makes titanium and iron stripping enter in the solution when acidleach goes out ilmenite as far as possible, chemical treatment leachate purification iron, titanium, by the doping zinc ion, adopt the sol-gel combustion synthesis process of citric acid complex to prepare composite oxide of metal novel photocatalysis material.
Summary of the invention
The object of the present invention is to provide a kind of novel photocatalysis material low-cost preparation of two kinds of valuable elements of iron in the ilmenite, titanium high added value, well behaved, ecological, environmental protective that fully utilizes.
A kind of method of preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method, processing step is:
A. pulverize ilmenite concentrate and obtain the powder that size distribution is 0.1～10 μ m;
B. (be ilmenite concentrate weight: the concentrated hydrochloric acid volume) weighing ilmenite concentrate and concentrated hydrochloric acid are put into closed container according to ore deposit acid ratio=1: 5～30, the control extraction temperature is 30～120 ℃, extraction time is 1～5h, and reaction finishes to filter and obtains the buff leachate, suitably handles leached mud;
C. slowly drip concentrated ammonia liquor and regulate the pH of leachate, control final pH value is 6～9, precipitates Fe, Ti ion in the leachate fully, and the precipitation ageing is 24h at least, then isolated by filtration and with repeatedly washing precipitation of deionized water;
D. using the red fuming nitric acid (RFNA) dissolution precipitation, add the 50wt.% aqueous citric acid solution subsequently, is 6～8 with the pH value of concentrated ammonia liquor regulator solution, stirs and obtains settled solution, and water-bath control reaction temperature is 60～80 ℃, and heating evaporation solution obtains wet gel; The mol ratio of citric acid consumption and metal ion (iron+titanium) is 2～3, and the consumption mol ratio of nitric acid and citric acid is 2～9; According to actual needs, add zinc nitrate in red fuming nitric acid (RFNA) dissolution precipitation liquid, (zinc ion of doping): the mol ratio of (iron ion+titanium ion) is 1～5, and the mol ratio of citric acid consumption and metal ion (zinc+iron+titanium) is 2～3.
E. wet gel is put in and carries out roasting in the resistance furnace: be warmed up to 100～130 ℃ of insulation 20～30min with 5～10 ℃/min, then be warmed up to 140～160 ℃ of insulation 5～10min with 1～2 ℃/min, be warmed up to 250～300 ℃ with 1～2 ℃/min subsequently, gel generation spontaneous combustion obtains elementary powder.Elementary powder is warmed up to 500～1000 ℃ of insulation 1～6h with 2～5 ℃/min obtains the photocatalysis powder material in resistance furnace.
The present invention is raw materials used to be: ilmenite concentrate, promptly the product of ilmenite after ore dressing is cheap, wide material sources.
The invention has the advantages that: the catalysis material particle of the present invention's preparation is tiny, the photocatalytic activity height, in ultraviolet and visible region stronger light absorption being arranged all, can be used for field of solar energy utilization such as photocatalysis and opto-electronic conversion, is a kind of new material with application prospect.The present invention fully utilizes iron in the ilmenite, two kinds of main elements of titanium, avoided the operation that is recycled of the useless accessory substance of iron content, the new technology of a low-cost preparation novel photocatalysis material is provided, has opened up new way for the comprehensive utilization of China's titanium iron ore deposit again simultaneously.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the photocatalysis powder of the embodiment of the invention 1 preparation.This figure illustrates the thing phase composition difference through the photocatalysis powder of different temperatures roasting preparation.Through the powder of 600 ℃/2h roasting, the crystallization imperfection contains a spot of amorphous component, and multiple iron titanium oxide is also deposited; Through the powder of 800 ℃/6h roasting, crystal grain is grown complete, and principal crystalline phase is Fe
2TiO
5With a small amount of rutile titanium dioxide.
Fig. 2 is the X ray diffracting spectrum of the photocatalysis powder of the embodiment of the invention 2 preparations.This figure illustrates the thing phase composition difference through the photocatalysis powder of different temperatures roasting preparation.Through the powder of 600 ℃/2h roasting, there is amorphous component in the crystallization imperfection, and multiple composite metal oxide is also deposited; Through the powder of 800 ℃/6h roasting, crystal grain is grown complete, and principal crystalline phase has zinc-iron oxides, titanium zinc oxide and a small amount of rutile titanium dioxide.
Fig. 3 is the uv-visible absorption spectra figure of the photocatalysis powder of the present invention's preparation.This figure illustrates that powder all has absorption at the ultraviolet region and the visible region of 250～600nm scope.
Fig. 4 is the photocatalysis powder of the present invention preparation photocatalysis decolorizing effect to methyl orange dye solution.This figure illustrates the photocatalysis decolorizing effect difference of the photocatalysis powder of process different temperatures roasting preparation to methyl orange solution.
The specific embodiment
Embodiment 1
The chemical composition of used ilmenite concentrate is among this embodiment: TiO
2=52.03 quality %, TFe=28.2 quality %, MgO=4.25 quality %, SiO
2=1.80 quality %, Al
2O
3=1.04 quality %, CaO=0.56 quality %, Na
2O=0.10 quality %, MnO=0.67 quality %.
The ilmenite concentrate that gathers after crushed size distribution at 0.1～10 μ m.Than=1/25 (being ilmenite concentrate weight/concentrated hydrochloric acid volume), weighing ilmenite concentrate and concentrated hydrochloric acid are put into closed container according to ore deposit acid, heating container and to control temperature be 90 ℃, and it is 3h that the control acidleach goes out the time.Filtration obtains the buff leachate, and deionized water repeatedly washs leached mud.Slowly drip concentrated ammonia liquor subsequently in leachate, continue leaching liquid, control final pH value is 7, precipitates Fe, Ti ion in the leachate fully.With the precipitation ageing 24h that generates, isolated by filtration and with repeatedly washing precipitation of deionized water then.The mol ratio that control citric acid consumption and GOLD FROM PLATING SOLUTION belong to total ion concentration is 2, the consumption mol ratio of nitric acid and citric acid is 3, with an amount of red fuming nitric acid (RFNA) dissolution precipitation, add an amount of 50wt.% aqueous citric acid solution again and carry out complexing, pH value with the concentrated ammonia liquor regulator solution is 8, stirring obtains yellow settled solution, and adopting water-bath control complex reaction temperature is 60 ℃, and last heating evaporation solution obtains wet gel.Wet gel is put in carries out roasting in the high temperature resistance furnace: be warmed up to 120 ℃ with 5 ℃/min, insulation 30min, gel foaming; Then be warmed up to 150 ℃ with 1 ℃/min, a large amount of gases are emitted in gel expansion charing; Be warmed up to 250 ℃ with 1 ℃/min subsequently, gel generation spontaneous combustion obtains elementary powder.Elementary powder is warmed up to 600 ℃ of insulation 2h with 2 ℃/min obtains photocatalysis powder sample 1 in resistance furnace; Elementary powder is warmed up to 800 ℃ of heat treatment 6h with 2 ℃/min obtains photocatalysis powder sample 2 in resistance furnace.
Photocatalytic activity test: put into the methyl orange aqueous solution that the 100ml initial concentration is 10mg/L and the photocatalysis powder 100mg of embodiment 1 preparation in beaker, ultrasonic wave disperses 30min behind the magnetic agitation 2h, obtains suspension system solution.With a 300W high-pressure sodium lamp is light source irradiation 60min.The photocatalytic degradation efficient of 1 pair of methyl orange solution of photocatalysis powder sample of present embodiment preparation is 57.03%; The photocatalytic degradation efficient of 2 pairs of methyl orange solutions of sample is 86.63%.
Embodiment 2
Initial feed that present embodiment is used and processing step are identical with embodiment 1.Than=1/20 (being ilmenite concentrate weight/concentrated hydrochloric acid volume), weighing ilmenite concentrate and concentrated hydrochloric acid are put into closed container according to ore deposit acid, heating container and to control temperature be 100 ℃, and it is 2.5h that the control acidleach goes out the time.Filtration obtains the buff leachate, and deionized water repeatedly washs leached mud.Slowly drip concentrated ammonia liquor subsequently in leachate, control final pH value is 9, precipitates Fe, Ti ion in the leachate fully.With the precipitation ageing 24h that generates, isolated by filtration and with repeatedly washing precipitation of deionized water then.The mol ratio of control (zinc ion of doping)/(iron ion+titanium ion) is 1, the mol ratio of citric acid consumption and metal ion (zinc+iron+titanium) total amount is 2, the consumption mol ratio of nitric acid and citric acid is 5, with an amount of red fuming nitric acid (RFNA) dissolution precipitation, adding an amount of zinc nitrate and an amount of 50wt.% aqueous citric acid solution subsequently respectively, is 7 with the pH value of concentrated ammonia liquor regulator solution, and stirring obtains yellow settled solution, adopting water-bath control complex reaction temperature is 65 ℃, and last heating evaporation solution obtains wet gel.Wet gel is put in carries out roasting in the high temperature resistance furnace: be warmed up to 120 ℃ with 5 ℃/min, insulation 20min, gel foaming; Then be warmed up to 150 ℃ with 1 ℃/min, insulation 5min, a large amount of gases are emitted in gel expansion charing; Be warmed up to 250 ℃ with 1 ℃/min subsequently, gel generation spontaneous combustion obtains elementary powder.Elementary powder is warmed up to 600 ℃ of insulation 2h with 2 ℃/min obtains photocatalysis powder sample 3 in resistance furnace; Elementary powder is warmed up to 800 ℃ of heat treatment 6h with 2 ℃/min obtains photocatalysis powder sample 4 in resistance furnace.The photocatalytic activity test is with embodiment 1, and the result shows that the photocatalytic degradation efficient of 3 pairs of methyl orange solutions of photocatalysis powder sample of present embodiment preparation is 60.21%; The photocatalytic degradation efficient of 4 pairs of methyl orange solutions of sample is 89.63%.
Claims (2)
1. method with preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method, it is characterized in that: processing step is:
A. pulverize ilmenite concentrate and obtain the powder that size distribution is 0.1～10 μ m;
B. sour than being ilmenite concentrate weight according to the ore deposit: concentrated hydrochloric acid volume=1: 5～30 weighing ilmenite concentrates and concentrated hydrochloric acid are put into closed container, and the control extraction temperature is 30～120 ℃, and extraction time is 1～5h, filters to obtain leachate;
C. slowly drip concentrated ammonia liquor and regulate the pH of leachate, control final pH value is 6～9, and the precipitation ageing is 24h at least, isolated by filtration and with repeatedly washing precipitation of deionized water;
D. using the red fuming nitric acid (RFNA) dissolution precipitation, add the 50wt.% aqueous citric acid solution subsequently, is 6～8 with the pH value of concentrated ammonia liquor regulator solution, stirs and obtains settled solution, and water-bath control reaction temperature is 60～80 ℃, and heating evaporation solution obtains wet gel; The mol ratio of citric acid consumption and metal ion (iron+titanium) is 2～3, and the consumption mol ratio of nitric acid and citric acid is 2～9;
E. wet gel is put in and carries out roasting in the resistance furnace: be warmed up to 100～130 ℃ of insulation 20～30min with 5～10 ℃/min, then be warmed up to 140～160 ℃ of insulation 5～10min with 1～2 ℃/min, be warmed up to 250～300 ℃ with 1～2 ℃/min subsequently, obtain elementary powder; Elementary powder is warmed up to 500～1000 ℃ of insulation 1～6h with 2～5 ℃/min obtains the photocatalysis powder material in resistance furnace.
2. a kind of method as claimed in claim 1 with preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method, it is characterized in that: in the d step, add zinc nitrate in the red fuming nitric acid (RFNA) dissolution precipitation liquid, (zinc ion of doping): the mol ratio of (iron ion+titanium ion) is 1～5, and the mol ratio of citric acid consumption and metal ion (zinc+iron+titanium) is 2～3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716501B (en) * | 2009-11-25 | 2012-04-18 | 广州远达环保科技有限公司 | Zinc titanate micro-nano photocatalysis material and preparation method thereof |
| CN102989457A (en) * | 2012-12-11 | 2013-03-27 | 常州大学 | Method for preparing photocatalytic material from waste titanium steel alloy |
| CN103920494A (en) * | 2014-04-04 | 2014-07-16 | 西华大学 | Wet type catalytic oxidation catalyst preparing method and applications of prepared catalyst |
| CN108479779A (en) * | 2018-04-10 | 2018-09-04 | 浙江工业大学温州科学技术研究院 | A kind of magnetic Fe2TiO5The preparation method of catalysis material |
-
2008
- 2008-04-03 CN CNB2008101033488A patent/CN100566826C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716501B (en) * | 2009-11-25 | 2012-04-18 | 广州远达环保科技有限公司 | Zinc titanate micro-nano photocatalysis material and preparation method thereof |
| CN102989457A (en) * | 2012-12-11 | 2013-03-27 | 常州大学 | Method for preparing photocatalytic material from waste titanium steel alloy |
| CN103920494A (en) * | 2014-04-04 | 2014-07-16 | 西华大学 | Wet type catalytic oxidation catalyst preparing method and applications of prepared catalyst |
| CN103920494B (en) * | 2014-04-04 | 2016-01-13 | 西华大学 | The application of the catalyst of catalytic wet oxidation method for preparing catalyst and preparation |
| CN108479779A (en) * | 2018-04-10 | 2018-09-04 | 浙江工业大学温州科学技术研究院 | A kind of magnetic Fe2TiO5The preparation method of catalysis material |
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Granted publication date: 20091209 Termination date: 20120403 |