CN102641731B - Active carbon fiber load calcium-doping titanium dioxide (TiO2) photocatalyst and preparation method of photocatalyst - Google Patents
Active carbon fiber load calcium-doping titanium dioxide (TiO2) photocatalyst and preparation method of photocatalyst Download PDFInfo
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Abstract
The invention discloses an active carbon fiber load calcium-doping titanium dioxide (TiO2) photocatalyst and a preparation method of the photocatalyst. The catalyst consists of active carbon fiber and calcium-doping TiO2 immobilized on the active carbon fiber. The cheap and easy-to-obtain calcium elements are adopted to be used as doping elements for improving the photocatalysis activity of TiO2, the capability for degrading organic contaminants is higher, the photocatalyst can be applicable to the degradation treatment of organic contaminants in waste water, in addition, higher photocatalysis activity can still be realized when the concentration of the organic contaminants in the waste water is low, the calcium elements are directly compounded on the TiO2, the secondary pollution problem is avoided, the preparation process is simple, the immobilization of the TiO2 on the surface of the active carbon fiber is firm, the serious falling phenomenon is avoided, the composite photocatalysis materials can be repeatedly used, and the photocatalysis efficiency basically maintains unchanged.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, relate in particular to a kind of preparation method of the titanium dioxide optical catalyst for the treatment of organic pollutants.
Background technology
Along with expanding economy, environmental pollution is more and more serious, and due to the modern industry waste water that all water body discharge towards periphery contains a large amount of organic pollutions, many organic pollutions contain biology is to strong inhibiting phenyl ring, be difficult to biodegradation, thereby make available water resource fewer and feweri.
Process at present that in the method for organic pollution of organism in water difficult degradation, to use more be photocatalytic oxidation.Photocatalytic oxidation is a kind of directly effective processing method, is more and more subject to people's attention, and especially utilizes titanium dioxide TiO
2semiconductor powder has become the focus of research as the catalytic oxidation new technology of photochemical catalyst.TiO
2photocatalysis oxidation technique has overcome the deficiency of many conventional methods, and has advantages of a lot: first, it can by Some Organic Pollutants contained in water degradable be CO
2, H
2o etc.; Secondly, TiO
2itself be nontoxic, and cheap stable performance; In addition, it does not need other electron acceptor, as H
2o
2; Finally, TiO
2the easy control of operating condition and the oxidability of photocatalysis oxidation technique are very strong.
But have two kinds of principal elements to limit the application of optically catalytic TiO 2: the one, nano-TiO
2particle is less, during use, very easily runs off, and is difficult to separated recovery, and when processing light concentration organic pollutant because of TiO
2particle around organic contamination substrate concentration compared with shortcomings such as low and photocatalysis efficiency are low; The 2nd: due to light induced electron-hole easily occur compound, so catalytic efficiency is low.
In order to solve nano-TiO
2recovery problem, generally all it is loaded on certain carrier.In conventional art, the load carriers material having adopted has woven wire, metal foam silk screen or inorganic mineral etc., and because the specific area of these carrier materials is less, the efficiency of catalytic reaction is not high.Activated carbon fiber (being called for short ACF) has higher specific area, becomes nano-TiO
2the ideal carrier of load.Nano-TiO
2load on that both have cooperative effect after activated carbon fiber surface: the suction-operated of the bigger serface of activated carbon fiber can enrichment pollutant, makes TiO
2particle surface forms relatively high pollutant levels, is conducive to photocatalytic degradation pollutant.As patent documentation CN1943850A processes this support type photocatalysis net for the colourity of paper waste.The mainly degraded for liquid phase phenol pollutant by this support type photocatalysis net of patent documentation CN100998934A.Patent documentation CN1943851A is by activated carbon fiber loaded nano-TiO
2photocatalysis net is applied to the processing of COD in waste water (COD).Patent documentation CN1973997A is by activated carbon fiber loaded nano-TiO
2photocatalysis net is applied in the processing of methylene blue liquid phase pollution.Also there is nano-TiO in above-mentioned carrying method
2the problem that the intensity of load of particle, Load Balanced and stability are inadequate.In order to improve intensity of load, patent documentation CN101579622A has proposed the method for activated carbon fiber pretreatment back loading.
In recent years, for improving TiO
2photocatalysis efficiency, prepares metal-doped nano-TiO
2photochemical catalyst is extremely paid attention to.As patent documentation CN1010209413A proposes the transition metal such as copper doped, Ni-V-Fe in nano titanium oxide; Patent documentation CN1820842A proposes blended nano titanium dioxide degradable organic pollutant catalyst; Patent documentation CN101045203A proposes a kind of compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and preparation method thereof; Patent documentation CN101015792 discloses titanium dioxide perforated micro-pipe photocatalyst and the manufacture method thereof of modified by silver.(the Combinatorial doping of TiO such as professor M.R.Hoffmann
2with platinum (Pt), chromium (Cr), vanadium (V), andnickel (Ni) to achieve enhanced photocatalytic activity with visible light irradiation, J.Mater.Res., 25 (2010), 149-158) at TiO
2the middle many kinds of metal ions that adulterates respectively, studies its ultraviolet catalytic active.(the Photocatalytic and photoelectrochemical properties of titania chloroplatinate (IV) such as H.Kisch, Chem.Rev., 230 (2002), 41-47.) prepared the high activity TiO of Pt ion doping
2photochemical catalyst.
In order to reduce the manufacturing cost of catalyst, (the catalytic performance research of complex oxide of alkaline earth such as Yan Jianhui, functional material, 2006,8 (37), 1280-1285) proposed the composite photo-catalyst of the Ca-Ti ore type of alkali earth metal doped nano titanium dioxide, the preparation method of employing is citric acid complex method, specifically by alkaline-earth metal (Ma, Ca, Sr and Ba) nitrate and TiCl
4after mixing, in agitator, mix with excessive citric acid, regulate pH value to be about 7, low-temperature heat, make solution become colloidal sol, continue transpiring moisture and become gel, (90 ℃ of vacuum drying, 80-90Pa) within 8～12 hours, obtain cellular xerogel, smash to pieces and porphyrize after, prior to ashing at 400 ℃ 4 hours, then calcination 4 hours under sintering temperature.Gained composite photo-catalyst be take methyl orange as probe, the degradation efficiency of alkaline-earth metal composite photo-catalyst is higher than simple nano titanium oxide, but the method in evaporation process various solutes because of the difference of density, can produce segregation and layering, cause the inhomogeneous of component, there is the situation that doping is inhomogeneous, and the problem that exists anion to remove, so photocatalytic degradation reaction rate is still lower.
Summary of the invention
The object of this invention is to provide a kind of activated carbon fiber loaded calcium titanium dioxide optical catalyst and preparation method thereof of mixing, the above-mentioned defect existing to overcome prior art.
The activated carbon fiber loaded calcium titanium dioxide optical catalyst of mixing of the present invention, by activated carbon fiber and the calcium titanium dioxide of mixing being fixed on activated carbon fiber, formed, described activated carbon fiber is carrier, mixing the load capacity of calcium titanium dioxide on activated carbon fiber is 0.75～1.30g/g activated carbon fiber, and preferred load capacity is 0.9～1.1g/g activated carbon fiber;
Described activated carbon fiber is selected from felted activated carbon fiber, active carbon fiber felt or viscose base activated carbon fiber felt;
The specific area of described felted activated carbon fiber is 780～1250m
2/ g, total hole volume 0.45～0.65cm
3/ g, can be selected from the product of Qinhuangdao Zi Chuan carbon fiber Co., Ltd;
Described titanium dioxide is selected from anatase crystal;
Ca/Ti=0.25～0.70mol%; Preferred Ca/Ti=0.25～0.45mol%;
The activated carbon fiber loaded preparation method who mixes calcium titanium dioxide optical catalyst of the present invention, comprises the steps:
(1) will mix calcium TiO 2 sol is coated on activated carbon fiber, the load capacity of calcium titanium dioxide on activated carbon fiber of mixing of controlling after dry desolvation is 0.75～1.30g/g activated carbon fiber, preferred load capacity is 0.9～1.1g/g activated carbon fiber, dry 10～14 hours desolvations at 50～80 ℃;
(2) load is had to the activated carbon fiber of mixing calcium TiO 2 sol, under nitrogen protection, 420～570 ℃ of calcinings 1～3 hour, preferred calcining heat was 460～480 ℃, be cooled to afterwards normal temperature, obtain mixing calcium titanium dioxide and be fixed on the composite photocatalyst material on activated carbon fiber;
Preferably, with 5～10 ℃/min heating rate, be warming up to 460～480 ℃ of calcinings 1.5～2.5 hours;
The described calcium TiO 2 sol of mixing is preparation like this:
(1) tetrabutyl titanate and ethanol are mixed according to weight ratio for 1: 2.5～1: 3.2, obtain transparent yellow solution A;
(2) in weight ratio=1 of water and ethanol: in 1.5～1: 4 mixed solution, add calcium chloride and catalyst nitric acid, obtain solution B, wherein: the concentration of calcium chloride is 4～12wt%, preferred 4.2～11.2wt%, HNO
3concentration be 2.0～6.5wt%;
(3) solution B is added drop-wise in solution A, under room temperature, ageing is 4～6 hours, obtains mixing calcium TiO 2 sol;
In step (3), the weight ratio of solution B and solution A is:
1: 1～1: 3, preferably 1: 1.6～1: 2.5.
Inventor finds, adopt calcium constituent cheap and easy to get as doped chemical to improve TiO
2photocatalytic activity, can improve under given conditions the light-catalyzed reaction speed of such catalyst; Loaded on the activated carbon fiber with high-specific surface area, the suction-operated of the bigger serface by activated carbon fiber is at TiO simultaneously
2surface enrichment pollutant, forms relatively high pollutant levels, to improve photocatalysis efficiency and the practicality of product.
Of the present invention loading on activated carbon fiber and the titanium dioxide optical catalyst of doping calcium constituent, makes the titanium dioxide of mixing calcium act synergistically with activated carbon fiber, has stronger degraded decomposing organic pollutant ability.
The present invention adopts sol-gel process to prepare TiO
2nano particle adds the salting liquid of metal ion in the process of preparation, then the gel of formation is dried, sintering.This method has avoided take the anion pollution problem that inorganic salts are raw material, does not need washing and filtering, does not produce a large amount of waste liquids, and this method is easy to realize doping, and the particle size of preparing is little, and metallic is at TiO
2in be evenly distributed, can effectively improve TiO
2photocatalysis efficiency.
Of the present invention loading on activated carbon fiber and the titanium dioxide optical catalyst of doping calcium constituent, the ability of degradable organic pollutant is stronger, applicable to the organic pollution in degradation treatment waste water, and when Organic Pollutants in Wastewater concentration is lower, still there is higher photocatalytic activity, calcium constituent direct combination is on titanium dioxide, there is not the problem of secondary pollution, preparation process is simple, titanium dioxide is in the surperficial fixation of activated carbon fiber, there is no serious obscission, composite photocatalyst material can be reused, and photocatalysis efficiency almost remains unchanged.
Accompanying drawing explanation
The XRD collection of illustrative plates of the product of Fig. 1 embodiment 1.
The activated carbon fiber loaded electron scanning micrograph of mixing calcium titanic oxide composite photochemical catalyst material of Fig. 2 embodiment 1.
The degradation effect figure of Fig. 3 embodiment 1 composite photocatalyst material to simulating pollution thing.
The degradation effect figure of Fig. 4 embodiment 2 composite photocatalyst materials to simulating pollution thing.
The degradation effect figure of Fig. 5 embodiment 3 composite photocatalyst materials to simulating pollution thing.
The degradation effect figure of Fig. 6 embodiment 4 composite photocatalyst materials to simulating pollution thing.
The degradation effect figure of Fig. 7 embodiment 5 composite photocatalyst materials to simulating pollution thing.
The degradation effect figure of Fig. 8 comparative example 1 composite photocatalyst material to simulating pollution thing.
The specific embodiment
Detection method:
Get 8ml colloidal sol vacuum drying 24h at 60 ℃ and obtain light yellow crystal shape thing, after pulverizing, roasting 2h at 470 ℃, obtains photochemical catalyst white powder, adopts energy disperse spectroscopy (EDS) to measure the Ca/Ti mol% of catalyst.
TiO
2the method of testing of load capacity: get TiO
2/ ACF composite photocatalyst material 0.2～0.5g weighs and is recorded as m1,800 ℃ of roasting 2h in Muffle furnace, and with the cooling rear taking-up sample of stove, only remaining white powder, residual without black fiber, and ACF is completely burnt and is lost, and remaining photochemical catalyst is recorded as m2.By weighing technique computational load amount:
Load capacity=m2 ÷ (m1-m2)
Composite photocatalyst material light-catalyzed reaction effect evaluation method: cut 80mm * 25mm composite photocatalyst material (about 0.5g), be suspended in the glass beaker of 1 liter, light source is that the main excitation wavelength of 8w uviol lamp is 254nm, and light source is apart from solution surface 10cm, and solution deep is 6cm.Using methylene blue or methyl orange aqueous solution as simulating pollution thing, and the initial concentration of original solution is 15mg/L, and initial COD value is 40mg/L.The sampling of 15min gap, gets supernatant liquor and measures its COD value after centrifugation, characterize the degradation rate D (%) of methylene blue with the COD clearance of methylene blue solution.
In embodiment, activated carbon fiber is called for short ACF.
Mix the preparation of calcium TiO 2 sol: at room temperature the tetrabutyl titanate of 700g is joined in the ethanol of 1772g, stir 30min, obtain the yellow solution A of homogeneous transparent; The nitric acid, the 95g anhydrous calcium chloride that by the water of the ethanol of 886g, 400g, 71g concentration, are at room temperature 65wt% fully mix, and obtain solution B; Under agitation, solution B is added drop-wise in solution A, obtains the colloidal sol of homogeneous transparent.At room temperature ageing of colloidal sol is stand-by after 4 hours.
Load and heat treatment: get 100g ACF (800m
2/ g, total hole volume 0.442cm
3/ g) be cut into bulk (80mm * 100mm), after deionized water for ultrasonic washing 30min, under 60 ℃ of conditions, drying and processing took out after 4 hours, entirely put in pallet, then the colloidal sol after above-mentioned ageing is poured on ACF equably, after its absorption is saturated, being placed in 60 ℃, baking oven dries 12 hours, then it is proceeded to and in tube furnace, carry out calcination processing: 5 ℃/min of heating rate, nitrogen flow is 30mL/min, reach after 470 ℃, calcining at constant temperature 2 hours, naturally cooling afterwards, under nitrogen protection, be cooled to normal temperature, obtain the composite photocatalyst material that ACF mixes calcium titanium dichloride load.
The Ca/Ti=0.42mol% of gained photochemical catalyst, Fig. 1 is shown in by the XRD collection of illustrative plates of photochemical catalyst; Composite photocatalyst material photocatalyst amount is 1.02g/gACF, and the electron scanning micrograph of composite photocatalyst material is shown in Fig. 2.
Composite photocatalyst material effect assessment experiment: from Fig. 3 photocatalysis effect, illumination reaction is after 40 minutes, and methylene blue solution decolours completely, and COD clearance reaches 93%; Fresh original solution is removed and be replaced by solution in reactor, then carry out the reaction of second stage, after 45 minutes, methylene blue solution decolours completely, and COD clearance reaches 91%; In phase III reaction, after 48 minutes, methylene blue solution decolours completely, and COD clearance reaches 88%; Fourth stage, can cause methylene blue solution in 52 minutes and decolour completely, and COD clearance reaches 84%.
Embodiment 2
Mix the preparation of calcium TiO 2 sol: according to the method that embodiment mono-is identical, prepare colloidal sol, difference is that the consumption of calcium chloride is 57g.
Load and heat treatment: according to the identical method of embodiment 1 and condition, carry out load and heat treatment obtains mixing the composite photocatalyst material of calcium titanium dioxide and ACF load.
The Ca/Ti=0.25mol% of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 1.02g/gACF.
Catalysis material application test: from Fig. 4 photocatalysis effect, illumination reaction is after 40 minutes, and COD clearance reaches 86.9%.
Embodiment 3
Mix the preparation of calcium TiO 2 sol: method and the condition identical with embodiment 1, difference is that the consumption of anhydrous calcium chloride is 152g.
Load and heat treatment: according to the identical method of embodiment 1 and condition, carry out load and heat treatment obtains mixing the composite photocatalyst material of calcium titanium dioxide and ACF load.
The Ca/Ti=0.67mol% of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 1.02g/gACF.
Catalysis material application test: from Fig. 5 photocatalysis effect, illumination reaction is after 40 minutes, and COD clearance reaches 81.2%.
Embodiment 4
Mix the preparation of calcium TiO 2 sol: the TiO 2 sol of mixing calcium according to the identical method of embodiment 1 and condition preparation.
Load and heat treatment: by the method that embodiment mono-is identical, carry out load and heat treatment, difference be TiO 2 sol consumption be in embodiment mono-colloidal sol consumption 75%.
The Ca/Ti=0.42mol% of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 0.75g/gACF.
Catalysis material application test: from Fig. 6 photocatalysis effect, illumination reaction is after 40 minutes, and COD clearance reaches 82.8%.
Embodiment 5
Mix the preparation of calcium TiO 2 sol: the TiO 2 sol of mixing calcium according to the identical method of embodiment 1 and condition preparation.
Load and heat treatment: by the method that embodiment mono-is identical, carry out load and heat treatment, difference be TiO 2 sol consumption be in embodiment mono-colloidal sol consumption 130%, in baking oven, baking temperature is 80 ℃, be 10 hours drying time.
The Ca/Ti mol%=0.42 of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 1.30g/gACF.
Catalysis material application test: from Fig. 7 photocatalysis effect, illumination reaction is after 40 minutes, and COD clearance reaches 77.1%.
Embodiment 6
Mix the preparation of calcium TiO 2 sol: at room temperature the tetrabutyl titanate of 700g is joined in the absolute ethyl alcohol of 2100g, stir 30min, obtain the yellow solution A of homogeneous transparent; The nitric acid, the 95g anhydrous calcium chloride that by the deionized water of the absolute ethyl alcohol of 600g, 400g, 36g concentration, are at room temperature 65wt% fully mix, and obtain solution B; Under agitation, solution B is added drop-wise in solution A, obtains the colloidal sol of homogeneous transparent.At room temperature ageing of colloidal sol is stand-by after 6 hours.
Load and heat treatment: get 100g ACF (1120m
2/ g, total hole volume 0.610cm
3/ g) be cut into bulk (80mm * 100mm), after deionized water for ultrasonic washing 40min, under 50 ℃ of conditions, drying and processing took out after 8 hours, entirely put in pallet, then the colloidal sol after above-mentioned ageing is poured on ACF equably, after its absorption is saturated, being placed in 50 ℃, baking oven dries 14 hours, then it is proceeded to and in tube furnace, carry out calcination processing: 10 ℃/min of heating rate, nitrogen flow is 30mL/min, reach after 570 ℃, calcining at constant temperature 1 hour, directly enter afterwards nature temperature-fall period, after being cooled to normal temperature under nitrogen protection, take out sample, obtain mixing the composite photocatalyst material of calcium titanium dioxide and ACF load.
The Ca/Ti=0.42mol% of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 1.0g/gACF.
Catalysis material effect assessment experiment: illumination reaction is after 40 minutes, and methylene blue solution decolours completely, and COD clearance reaches 79.4%.
Embodiment 7
Mix the preparation of calcium TiO 2 sol: at room temperature the tetrabutyl titanate of 700g is joined in the absolute ethyl alcohol of 1772g, stir 30min, obtain the yellow solution A of homogeneous transparent; The nitric acid, the 95g anhydrous calcium chloride that by the deionized water of the absolute ethyl alcohol of 800g, 200g, 107g concentration, are at room temperature 65wt% fully mix, and obtain solution B; Under agitation, solution B is added drop-wise in solution A, obtains the colloidal sol of homogeneous transparent.At room temperature ageing of colloidal sol is stand-by after 4 hours.
Load and heat treatment: get 100g ACF (1120m
2/ g, total hole volume 0.610cm
3/ g) be cut into bulk (80mm * 100mm), after deionized water for ultrasonic washing 20min, under 80 ℃ of conditions, drying and processing took out after 4 hours, entirely put in pallet, then the colloidal sol after above-mentioned ageing is poured on ACF equably, after its absorption is saturated, being placed in 50 ℃, baking oven dries 12 hours, then it is proceeded to and in tube furnace, carry out calcination processing: 5 ℃/min of heating rate, nitrogen flow is 30mL/min, reach after 420 ℃, calcining at constant temperature 3 hours, directly enter afterwards nature temperature-fall period, after being cooled to normal temperature under nitrogen protection, take out sample, obtain mixing the composite photocatalyst material of calcium titanium dioxide and ACF load.
The Ca/Ti=0.42mol% of gained photochemical catalyst, composite photocatalyst material photocatalyst amount is 1.0g/gACF.
Catalysis material effect assessment experiment: illumination reaction is after 40 minutes, and methylene blue solution decolours completely, and COD clearance reaches 78.5%.
Comparative example 1
The preparation of TiO 2 sol: method and the condition identical with embodiment mono-, difference is not add anhydrous calcium chloride.
Load and heat treatment: according to the identical method of embodiment mono-and condition, carry out load and heat treatment obtains mixing the composite photocatalyst material of calcium titanium dioxide and ACF load.
Gained composite photocatalyst material photocatalyst amount is 1.02g/gACF.
Catalysis material application test: from Fig. 8 photocatalysis effect, illumination reaction is after 40 minutes, and COD clearance is 74%.
Claims (5)
1. the activated carbon fiber loaded calcium titanium dioxide optical catalyst of mixing, is characterized in that, activated carbon fiber and the calcium titanium dioxide of mixing being fixed on activated carbon fiber, consists of;
Mixing the load capacity of calcium titanium dioxide on activated carbon fiber is 0.75～1.30g/g activated carbon fiber;
Described activated carbon fiber is selected from felted activated carbon fiber or active carbon fiber felt, and the specific area of described felted activated carbon fiber is 780～1250m
2/ g, total hole volume 0.45～0.65cm
3/ g; Ca/Ti=0.25～0.45mol%.
2. the activated carbon fiber loaded calcium titanium dioxide optical catalyst of mixing according to claim 1, it is characterized in that mixing the load capacity of calcium titanium dioxide on activated carbon fiber is 0.9～1.1g/g activated carbon fiber.
3. according to the activated carbon fiber loaded preparation method who mixes calcium titanium dioxide optical catalyst described in claim 1～2 any one, it is characterized in that, comprise the steps:
(1) will mix calcium TiO 2 sol and be coated on activated carbon fiber, dry 10～14 hours desolvations at 50～80 ℃;
(2) load is had to the activated carbon fiber of mixing calcium TiO 2 sol, under nitrogen protection, 420～570 ℃ of calcinings 1～3 hour, be cooled to afterwards normal temperature, obtain mixing calcium titanium dioxide and be fixed on the photochemical catalyst on activated carbon fiber.
4. method according to claim 3, is characterized in that, with 5～10 ℃/min heating rate, is warming up to 460～480 ℃ of calcinings 1.5～2.5 hours.
5. method according to claim 3, is characterized in that, the described calcium TiO 2 sol of mixing is preparation like this:
(1) tetrabutyl titanate and ethanol are mixed according to weight ratio 1:2.5～1:3.2, obtain solution A;
(2) in the mixed solution of the weight ratio=1:1.5～1:4 of water and ethanol, add calcium chloride and catalyst nitric acid, obtain solution B, wherein: the concentration of calcium chloride is 4.2～11.2wt%, HNO
3concentration be 2.0～6.5wt%;
(3) solution B is added drop-wise in solution A, under room temperature, ageing is 4～6 hours, obtains mixing calcium TiO 2 sol;
In step (3), the weight ratio of solution B and solution A is 1:1.6～1:2.5.
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| CN103752333B (en) * | 2014-01-22 | 2016-03-16 | 西安工程大学 | The preparation method of nitrogen-doped nanometer titanium dioxide supported active carbon fiber composite |
| CN104923206A (en) * | 2015-06-11 | 2015-09-23 | 天津科技大学 | Composite photocatalyst used for degrading formaldehyde gas and preparation method of wood activated carbon fiber photocatalytic composite material for carrying composite photocatalyst |
| CN106083210A (en) * | 2016-06-25 | 2016-11-09 | 王赞 | Using method for the titanium oxide sol of ceramic tile |
| CN106215919A (en) * | 2016-07-25 | 2016-12-14 | 浙江沁园水处理科技有限公司 | A kind of photocatalyst carbon rod and its preparation method and application |
| CN110918080B (en) * | 2019-12-11 | 2022-10-18 | 景德镇陶瓷大学 | Carbon-doped CaTi 2 O 5 Preparation method of powder high-efficiency photocatalyst and product prepared by same |
| CN112495348B (en) * | 2020-11-11 | 2023-03-24 | 陕西浦士达环保科技有限公司 | Activated carbon capable of removing trichloromethane |
| CN113145159B (en) * | 2021-03-31 | 2023-03-10 | 郑州师范学院 | Biodiesel catalyst and preparation method thereof |
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| CN1943850A (en) * | 2006-10-13 | 2007-04-11 | 中国石油大学(华东) | Carbon base optic catalytic material for removing chromaticity of paper-making waste water and its preparing method and using method |
| CN100998934A (en) * | 2006-10-13 | 2007-07-18 | 中国石油大学(华东) | Loading type photocatalyst for treating phenol liguid phase pollutant and its preparation method and application |
| CN101045203A (en) * | 2007-04-29 | 2007-10-03 | 华南农业大学 | Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method |
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| CN100998934A (en) * | 2006-10-13 | 2007-07-18 | 中国石油大学(华东) | Loading type photocatalyst for treating phenol liguid phase pollutant and its preparation method and application |
| CN101045203A (en) * | 2007-04-29 | 2007-10-03 | 华南农业大学 | Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method |
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