CN100357021C - Process of preparing photocatalyst material with concentrated ilmenite - Google Patents
Process of preparing photocatalyst material with concentrated ilmenite Download PDFInfo
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- CN100357021C CN100357021C CNB2006100121232A CN200610012123A CN100357021C CN 100357021 C CN100357021 C CN 100357021C CN B2006100121232 A CNB2006100121232 A CN B2006100121232A CN 200610012123 A CN200610012123 A CN 200610012123A CN 100357021 C CN100357021 C CN 100357021C
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Abstract
The present invention relates to a method for preparing photocatalyst material with ilmenite ore concentrate, which belongs to the technical field of new photocatalyst material. The present invention has the processing steps of ilmenite ore concentrate pulverization, proportioning, ball milling, desiccation, forming, calcination, cooling and fine powder grinding for testing photocatalyst activity. The present invention has the advantages that the prepared novel photocatalyst powder is formed by compounding perovskite, spinel, inverse spinel, rutile and other oxide semiconductors with high photocatalyst activity and visible light response, the particle sizes of the photocatalyst powder are distributed in micrometre sizes, and the photocatalyst with the micrometer particle sizes also has high photocatalytic activity and is easily recovered from a suspension system for reuse. The preparation method has the advantages of simple manufacturing process, low cost, good photocatalyst performance of the prepared photocatalyst material and conformity with the requirements of environmental protection; the present invention provides a way for preparing products with high added value with the natural ilmenite ore concentrate.
Description
Technical field
The invention belongs to the photocatalyst new material technology field, a kind of method with preparing photocatalyst material with concentrated ilmenite particularly is provided.
Background technology
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, are with a wide range of applications for the feedstock production high-performance composite materials with the ilmenite.Whole development utilizes natural ilmenite to prepare high value added product, makes its increment, produces bigger economic results in society, follows the sustainable development of green ecological environment.
Concentrated ilmenite selecting and purchasing from ilmenite or titanomagnetite is come out, and raw material sources are extensive.Be the titanium that obtains through gravity treatment, magnetic separation or electric separation by the slag behind the selected iron and iron content all than higher addition product, general primary raw materials as preparation titanium dioxide, synthetic rutile, high titanium slag etc.The production method of titanium dioxide mainly contains sulfuric acid process and chloridising, sulfuric acid process exists that the three wastes are many, energy consumption is high and problem such as product quality is low, though the chloridising flow process is short, environmental pollution is less relatively, generally will be with artificial rutile as raw materials for production, to titanium purity requirement in the raw material than higher.In a word, at present utilize the approach cost performance not high to concentrated ilmenite.
By photochemical catalytic oxidation reduction effect degraded noxious pollutant, non-secondary pollution is the environmental type catalysis technique with exploitation future.The research of photocatalyst of titanium dioxide is the most extensive, the restriction of wavelength but photocatalyst of titanium dioxide is stimulated in actual applications.Because TiO
2Energy gap be 3.2eV, corresponding excitation wavelength belongs to ultraviolet region at 387nm, and economical and practical photocatalyst material should be able to utilize visible light part abundant in the sunshine.One of method of dealing with problems is that photocatalyst of titanium dioxide is carried out modification, and it two is exactly to research and develop novel photocatalyst material, and seeking economical and practical novel photocatalyst material becomes a new research focus.Had bibliographical information by transition metal iron doped Ti O
2, semiconductor Fe
2O
3Composite Ti O
2, magnetic semiconductor Fe
3O
4Composite Ti O
2, semiconductor ZnO composite Ti O
2, preparation modification TiO
2Photocatalyst material.Also bibliographical information has been arranged with zinc titanate ZnTiO
3Or spinelle ZnFe
2O
4As photocatalyst material photocatalytic degradation pollutant, have higher photocatalytic activity and reach the visible light sensitivity.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 photocatalyst materials of three kinds of different structures, have visible light utilization rate height, characteristics that photocatalysis efficiency is high, have broad application prospects at aspect such as dispose of sewage, purify air, and kind is numerous, is expected to filter out photocatalyst more efficiently.
Comprehensive above research information, we have produced integral body and have utilized valuable element in the natural concentrated ilmenite to prepare the idea of heterogeneous compound novel photocatalyst material.Taked solid phase reaction roasting method simple to operate, preparation low cost, high-performance, high value-added product provide a brand-new route that efficiently utilizes natural ilmenite.
Summary of the invention
The purpose of this invention is to provide a kind of method with preparing photocatalyst material with concentrated ilmenite, integral body utilizes natural concentrated ilmenite to prepare high value added product, has realized that preparation technology is simple, and with low cost, photocatalysis performance is good, the photocatalyst material of ecological, environmental protective.
The present invention is raw materials used to be: titanium and all higher concentrated ilmenite of iron content that the slag behind the selected iron obtains through gravity treatment, magnetic separation, and cheap, wide material sources; Introduce a certain amount of zinc oxide.
Processing step of the present invention is:
A. raw material pulverizing: pulverize concentrated ilmenite with the electromagnetism sampling machine, obtain the powder that size distribution is 0.3～20 μ m;
B. prepare burden: concentrated ilmenite=50～95 quality %, zinc oxide=5～50 quality %;
C. ball milling: with the absolute ethyl alcohol is abrasive media, batching ball milling 5～10h in ball grinder;
D. dry: the material behind the ball milling is put into baking oven, carries out drying under 60～80 ℃ of temperature;
E. shaped by fluid pressure: take by weighing dried material and pack in the mould compression moulding under 30～60MPa pressure into;
F. roasting: roasting under air atmosphere and normal pressure, sintering temperature are at 400～1200 ℃, and heating rate is 1～3 ℃/min, and temperature retention time is 1～10h, and insulation finishes and naturally cools to room temperature;
G. grind: the block product after the roasting is pulverized, and the granularity of grinding the back micro mist is at 0.1～15 μ m.
The photocatalytic activity method of testing of the serial photocatalyst powder of preparation:
As the photocatalytic degradation object, the serial photocatalyst powder of preparation is excitation source as photochemical catalyst with the 300W high-pressure sodium lamp with organic dyestuff methyl orange.Process of the test is: in quartz cell, put into the methyl orange aqueous solution of 100ml variable concentrations, different pH values and the serial photocatalyst powder of different amounts, and the ultrasonic supending photocatalysis system that is uniformly dispersed, the adjusting radiation source is 10～20cm to the distance of liquid level.With oxygen increasing pump air-blowing in suspension, open light source irradiation different time after several minutes earlier.Suspension behind the photocatalytic degradation is separated with centrifuge,, get the centrifuge tube clear liquid photocatalytic degradation rate that is used to test methyl orange solution at the middle and upper levels with the centrifugal speed centrifugation twice of 2000～4000r/min.
The invention has the advantages that: the novel photocatalyst powder of preparation is to be composited mutually by Ca-Ti ore type, spinelle and inverse spinel structure, rutile and the multiple thing of other oxide semiconductor, and the photocatalytic activity height is visible light-responded; The granularity of photocatalyst powder is a micron-scale, and the photocatalyst of micron grade has higher photocatalytic activity equally, and easily recycles and reuses from suspension system.This preparation method's technology is simple, with low cost, and the photocatalyst material photocatalysis performance of preparation is good, meets environment protection requirement, provides an integral body to utilize natural concentrated ilmenite to prepare the approach of high value added product.
Can make novel environment friendly materials such as coating, block or coating with the serial photocatalyst powder of the present invention's preparation with photocatalysis performance.
Description of drawings
Figure l for the sample of concentrated ilmenite=80 quality % in the present invention batching and ZnO=20 quality % at 800 ℃ of XRD material phase analysis figure that are incubated the photocatalyst powder that 2h make.This figure illustrates that the photocatalyst powder of preparation is to be composited mutually by Ca-Ti ore type, spinelle and inverse spinel structure, rutile and the multiple thing of other oxide semiconductor.
The particle size distribution figure of the photocatalyst powder that Fig. 2 makes at 800 ℃ of insulation 2h for the sample of concentrated ilmenite=80 quality % in the present invention batching and ZnO=20 quality %.This figure illustrates that the photocatalyst powder granularity of preparation is a micron-scale.
Fig. 3 is the UV, visible light diffuse reflection absorption spectrum curve of the serial photocatalyst powder of the present invention's preparation: (a) concentrated ilmenite=90 quality % and ZnO=10 quality %, and sample is at 500 ℃ of insulation 2h; (b) concentrated ilmenite=70 quality % and ZnO=30 quality %, sample is at 600 ℃ of insulation 1h; (c) concentrated ilmenite=80 quality % and ZnO=20 quality %, sample is at 800 ℃ of insulation 2h.This figure illustrates that the serial photocatalyst powder of preparation has strong absorption at visible region.
The specific embodiment
Embodiment 1
The chemical composition of used concentrated ilmenite is among this embodiment: TiO
2=43.89 quality %, Fe
2O
3=40.09 quality %, MgO=4.36 quality %, SiO
2=4.00 quality %, Al
2O
3=2.12 quality %, CaO=0.81 quality %, SO
3-0.78 quality %, MnO=0.59 quality %, other component content occupy 3.36 quality %.
The concentrated ilmenite of gathering is pulverized, and the concentrated ilmenite raw material granularity after pulverizing with the electromagnetism sampling machine is distributed in 0.3～20 μ m, and the meta particle diameter is 2.95 μ m.Concentrated ilmenite is pulverized the back and carry out drying in baking oven.Introduce zinc oxide and prepare burden, concentrated ilmenite=80 quality % wherein, ZnO=20 quality %, zinc oxide are that chemical analysis is pure.As abrasive media, ball milling 7h in ball grinder prepares burden with absolute ethyl alcohol.Compound behind the ball milling is dry under 80 ℃ of temperature.Take by weighing the dried material of 8.0g and pack in the mould, be pressurized to 50MPa, the moulding sample is the round pie block.Sample is placed in the alumina crucible, roasting in tube type high-temperature furnace, sintering temperature is 600 ℃, and heating rate is 2 ℃/min, and temperature retention time is 1h, naturally cools to room temperature subsequently.Block goods after the roasting are pulverized, ground and obtain the photocatalyst powder.
Photocatalytic activity test: put into the methyl orange aqueous solution that the 100ml initial concentration is 5mg/L, pH=3.00 and the 500mg photocatalyst powder of embodiment 1 preparation in quartz cell, ultrasonic dispersion 30min obtains suspension system solution, adds 0.2ml H again
2O
2=5 volume %.With a 300W high-pressure sodium lamp is the light source irradiation, light source distance liquid level 20cm.With oxygen increasing pump air-blowing in suspension, open light source irradiation 60min in the photocatalytic degradation process.The photocatalyst powder of present embodiment preparation is 82.45% to the photocatalytic degradation rate of methyl orange solution.
Embodiment 2
Initial feed that present embodiment is used and processing step are identical with embodiment 1, and that different is concentrated ilmenite=90 quality % in the batching, ZnO=10 quality %; Sintering temperature is 500 ℃, and temperature retention time is 2h; The photocatalyst powder of photocatalytic activity test shows present embodiment preparation is 72.89% to the photocatalytic degradation rate of methyl orange solution.
Embodiment 3
Initial feed that present embodiment is used and processing step are identical with embodiment 1, and that different is concentrated ilmenite=80 quality % in the batching, ZnO=20 quality %; Sintering temperature is 800 ℃, and temperature retention time is 2h; The photocatalyst powder of photocatalytic activity test shows present embodiment preparation is 59.66% to the photocatalytic degradation rate of methyl orange solution.
Claims (1)
1, a kind of method with preparing photocatalyst material with concentrated ilmenite, it is characterized in that: processing step is:
A. raw material pulverizing: pulverize concentrated ilmenite with the electromagnetism sampling machine, obtain the powder that size distribution is 0.3～20 μ m;
B. prepare burden: concentrated ilmenite=50～95 quality %, zinc oxide=5～50 quality %;
C. ball milling: with the absolute ethyl alcohol is abrasive media, batching ball milling 5～10h in ball grinder;
D. dry: the material behind the ball milling is put into baking oven, carries out drying under 60～80 ℃ of temperature;
E. shaped by fluid pressure: take by weighing dried material and pack in the mould compression moulding under 30～60MPa pressure into;
F. roasting: roasting under air atmosphere and normal pressure, sintering temperature are at 400～1200 ℃, and heating rate is 1～3 ℃/min, and temperature retention time is 1～10h, and insulation finishes and naturally cools to room temperature;
G. grind: the block product after the roasting is pulverized, and the granularity of grinding the back micro mist is at 0.1～15 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100121232A CN100357021C (en) | 2006-06-06 | 2006-06-06 | Process of preparing photocatalyst material with concentrated ilmenite |
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|---|---|---|---|
| CNB2006100121232A CN100357021C (en) | 2006-06-06 | 2006-06-06 | Process of preparing photocatalyst material with concentrated ilmenite |
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|---|---|
| CN1857768A CN1857768A (en) | 2006-11-08 |
| CN100357021C true CN100357021C (en) | 2007-12-26 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111790368B (en) * | 2020-07-08 | 2023-02-03 | 安徽徽光电子科技有限公司 | Preparation process of photocatalyst self-cleaning material |
| CN113101912B (en) * | 2021-04-16 | 2021-11-05 | 海南浦金科技有限责任公司 | Method for preparing magnetic TiO by ball milling ilmenite2Method for preparing photocatalyst and magnetic TiO obtained2Application of |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288779A (en) * | 2000-09-21 | 2001-03-28 | 上海交通大学 | Composite nanometer titanium dioxide/iron powder catalyst and its preparation |
| CN1493394A (en) * | 2002-10-31 | 2004-05-05 | 中国科学院广州能源研究所 | Iron oxide enveloped titanium dioxide photocatalyst and its preparation method and use |
| WO2004052533A1 (en) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Production of magnetic titanium dioxide particles |
| JP2005279545A (en) * | 2004-03-30 | 2005-10-13 | National Institute Of Advanced Industrial & Technology | Photocatalyst |
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2006
- 2006-06-06 CN CNB2006100121232A patent/CN100357021C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288779A (en) * | 2000-09-21 | 2001-03-28 | 上海交通大学 | Composite nanometer titanium dioxide/iron powder catalyst and its preparation |
| CN1493394A (en) * | 2002-10-31 | 2004-05-05 | 中国科学院广州能源研究所 | Iron oxide enveloped titanium dioxide photocatalyst and its preparation method and use |
| WO2004052533A1 (en) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Production of magnetic titanium dioxide particles |
| JP2005279545A (en) * | 2004-03-30 | 2005-10-13 | National Institute Of Advanced Industrial & Technology | Photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 二氧化钛可见光光催化剂研究进展 唐剑文，吴平霄，曾少雁等.现代化工，第25卷第2期 2005 * |
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Granted publication date: 20071226 Termination date: 20110606 |