CN101574656A - Nanometer cobalt ion-doped titanic anhydride catalyst and preparation method thereof - Google Patents
Nanometer cobalt ion-doped titanic anhydride catalyst and preparation method thereof Download PDFInfo
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- CN101574656A CN101574656A CNA2009100723279A CN200910072327A CN101574656A CN 101574656 A CN101574656 A CN 101574656A CN A2009100723279 A CNA2009100723279 A CN A2009100723279A CN 200910072327 A CN200910072327 A CN 200910072327A CN 101574656 A CN101574656 A CN 101574656A
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Abstract
The invention discloses a nanometer cobalt ion-doped titanic anhydride catalyst and a preparation method thereof, which relates to a titanic anhydride catalyst and a preparation method thereof. The invention solves the problem of difficult improvement of TOC removal rate of the yielding water during the water treatment process by the existing advanced oxidation technique. The catalyst of the invention is prepared by butyl titanate, absolute ethyl alcohol, cobalt chloride, concentrated chlorhydric acid and distilled water. The preparation method comprises the following steps of: 1. dripping the butyl titanate into the absolute ethyl alcohol under magnetic stirring; 2. continuously stirring the solution for 1h, then dripping the concentrated chlorhydric acid and adding the cobalt chloride successively and continuously stirring the solution until the solution is clear; 3. continuously stirring the solution for 90 min, dripping the distilled water and conducting static ageing; 4. drying and grinding; and 5. sintering to obtain the catalyst. The catalyst of the invention has the advantages of good activity and high stability and can effectively reduce the TOC of yielding water. The preparation method of the invention has simple technique and convenient operation.
Description
Technical field
The present invention relates to a kind of titanium deoxide catalyst and preparation method thereof, described catalyst is mainly used in organic pollution in the catalytic ozonation degradation drinking water.
Background technology
In recent years, along with developing rapidly of industrial or agricultural level and improving constantly of living standards of the people, it has been common problem that the Drinking Water in China water source is subjected to severe contamination.A large amount of poisonous and hazardous organic pollutions such as agricultural chemicals, chemical products and other all kinds of artificial chemicals enter natural water, comprising " persistence organic pollutant (POPs) " and " incretion interferent (ECDs) ".Above-mentioned organic matter has caused huge threat to hydrobiological living environment in natural water, simultaneously itself for the mankind, multiple organic matter can not effectively be removed by traditional common process owing to have feature such as low concentration, high harm and high stability, and in the disinfecting process in water factory, as cholorination, produced a large amount of poisonous and hazardous DBPs, human existence health status has been produced huge negative.Therefore, under drinking water source is subjected to threat that organic contamination constantly increases the weight of, improve drinking water quality effectively thereby study the novel technology that can effectively remove micro-hardly degraded organic substance in the water, the sustainable development of China is just had extremely important strategic importance.Ozone has obtained using widely in drinking water and wastewater treatment as a kind of strong oxidizer.But because it has certain selectivity on oxidation of organic compounds, can only oxidize water in a part of organic pollution, so the large-scale application of ozone has certain limitation.Compare common process and independent ozonisation, the catalytic ozonation technology, thereby promptly remove a kind of high-level oxidation technology (AOPs) of various organic pollutions in the water effectively, be considered to a kind of water technology with broad prospect of application by the hydroxyl radical free radical that produces strong oxidizing property.Compare with the ozonisation organic matter, the hydroxyl radical free radical of generation can be rapidly and organic pollution in the non-selectivity oxidize water efficiently.
The heterocatalysis ozonisation is a kind of as catalytic ozonation, is to decompose as catalyst ozone with metal, metal oxide or other solid matters, produces organic matter in the hydroxyl radical free radical oxidize water.As a kind of semiconductor alloy, characteristics such as nontoxic, inexpensive and stable performance are widely used in industry-by-industry to titanium dioxide because of it, then often as catalyst or catalyst carrier, and its research work mainly concentrated on photochemical catalytic oxidation in the high-level oxidation technology in water treatment.Yet studies have shown that titanium dioxide can produce hydroxyl radical free radical by catalysis ozone under the condition of not having ultraviolet ray (UV), the organic pollution of stable existence is had good degradation effect.Nano level titanium dioxide advantageous properties such as specific area becomes greatly, the surface atom coordination is complete, the change of surface-active position is many occur, thereby has more the activity that higher catalysis ozone decomposes, thereby more and more paid close attention to and study along with particle diameter reduces.Yet further studies show that to Nano titanium dioxide catalytic ozonation degrading nitrobenzene, though this catalyst has very high clearance at catalytic ozonation for nitrobenzene, but decompose the intermediate product that generates for nitrobenzene oxidation, as various little carboxylic acids, there is not good effect of removing, therefore caused the accumulation of intermediate product in oxidizing process, thereby caused TOC of yielding water (total organic carbon) clearance to be difficult to improve, not from reaching the deep purifying of drinking water in essence.
Summary of the invention
The objective of the invention is the problem that is difficult to improve for the clearance that solves TOC of yielding water in the existing high-level oxidation technology water treatment procedure, and a kind of nanometer cobalt ion-doped titanic anhydride catalyst and preparation method thereof is provided.Good catalyst activity of the present invention and stability are high, thereby can catalytic ozonation produce hydroxyl radical free radical and improve stable contaminant degradation rate in the water significantly, and can significantly strengthen the degree of depth of intermediate oxidation products such as little carboxylic acids is degraded, reduce TOC of yielding water effectively.
Nanometer cobalt ion-doped titanic anhydride catalyst is to be made by butyl titanate, absolute ethyl alcohol, cobalt chloride, concentrated hydrochloric acid and distilled water among the present invention, wherein butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, the volume ratio of distilled water and Butyl Phthalate is 5: 6.
The preparation method of nanometer cobalt ion-doped titanic anhydride catalyst is undertaken by following step among the present invention: in the time of one, with 200～250r/min speed magnetic agitation butyl titanate is splashed in the absolute ethyl alcohol, butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the time that drips butyl titanate is 12～15min, dropwises the back and continues to stir; Two, drip concentrated hydrochloric acid (making inhibitor) in the reactant liquor of first butyl titanate drippage back 60min after step 1 is handled, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, the time that drips concentrated hydrochloric acid is 1～2min, add cobalt chloride subsequently, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, continue to stir; Three, drip distilled water (making gelatinizing agent) in the reactant liquor after step 2 is handled behind first butyl titanate drippage 90min, the volume ratio of distilled water and Butyl Phthalate is 5: 6, dripping the distilled water time is 12～15min, dropwises and obtains gel, again with the static ageing 0.5～2h of gel; Four, the gel after the ageing is put into baking oven, dry 3h under 100～105 ℃ condition becomes nanometer grade powder again after grinding; Five, nanometer grade powder is put into Muffle furnace, be warming up to 500 ℃ with 2 ℃/min speed, knot 2h reburns; Promptly obtain the nanometre grade cobalt doping titanium dioxide catalyst.
Nanometer cobalt ion-doped titanic anhydride catalyst of the present invention is mainly used in the catalytic ozonation Drinking Water; Can adopt existing catalytic ozonation method to handle, catalyst adopts disposable dosing method in the aforementioned catalytic ozonation method, and ozone adds continuously, process conditions: the ozone flux is 7mg/min, and the dosage of catalyst is 0.1mg/L.Under the same conditions, TOC of yielding water clearance of the present invention has improved more than 27.4% than ozone oxidation method, compares TiO
2The catalytic ozonation method has improved more than 22%.
Compared with prior art, the present invention has following advantage:
1, catalyst of the present invention adopts Prepared by Sol Gel Method, makes Co
X+Be evenly distributed to TiO
2In the lattice.
2, catalyst of the present invention passes through Co
X+To TiO
2Doping, change TiO
2Surfaces characteristic such as crystalline structure, surface functional group, surface hydroxyl, promoting that ozone decomposes on the basis of the hydroxyl radical free radical that generates strong oxidizing property in water, improved catalytic activity simultaneously, thereby realized significantly raising the TOC of yielding water removal to intermediate products such as little carboxylic acids.
3, catalyst applied range of the present invention can the catalytic ozonation removal be drunk the underwater trace persistent organic pollutants in pH value=2～12 scopes.
4, catalyst of the present invention is good and stable high, thereby can catalytic ozonation produce hydroxyl radical free radical and improve stable contaminant degradation rate in the water significantly, and can significantly strengthen the degree of depth of intermediate oxidation products such as little carboxylic acids is degraded, reduce TOC of yielding water effectively.
5, preparation method of the present invention is simple, and is with low cost, can reduce the cost of catalytic ozonation Drinking Water, and is difficult for causing secondary pollution.
Description of drawings
Fig. 1 is the specific embodiment ten a pair of TOC of yielding water clearance curve maps, among Fig. 1-and ■-expression ozone oxidation TOC of yielding water clearance curve ,-●-expression TiO
2Catalytic ozonation TOC of yielding water clearance curve ,-▲-expression Co
X+Doped Ti O
2Catalytic ozonation TOC of yielding water clearance curve; Fig. 2 is the clearance curve map of the specific embodiment 11 p-nitrophenyls, among Fig. 2-and the clearance curve of ■-expression ozone oxidation nitrobenzene ,-●-expression TiO
2The clearance curve of catalytic ozonation nitrobenzene ,-▲-expression Co
X+Doped Ti O
2Catalytic ozonation TOC of yielding water clearance curve.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the present embodiment nanometer cobalt ion-doped titanic anhydride catalyst is to be made by butyl titanate, absolute ethyl alcohol, cobalt chloride, concentrated hydrochloric acid and distilled water, wherein butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, the volume ratio of distilled water and Butyl Phthalate is 5: 6.
The particle diameter of the described catalyst of present embodiment is a nanoscale.The described nanometer cobalt ion-doped titanic anhydride catalyst of present embodiment is mainly used in the catalytic ozonation Drinking Water, can adopt existing catalytic ozonation method to handle, catalyst adopts disposable dosing method in the aforementioned catalytic ozonation method, ozone adds continuously, its process conditions: the ozone flux is 7mg/min, and the dosage of catalyst is 0.1mg/L.Under the same conditions, present embodiment TOC of yielding water clearance has improved more than 27.4% than ozone oxidation method, compares TiO
2The catalytic ozonation method has improved more than 22%.And the catalyst applied range of present embodiment can the catalytic ozonation removal be drunk the underwater trace persistent organic pollutants in pH value=2～12 scopes.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the mass fraction of described concentrated hydrochloric acid is 36.5%.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is: in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 15～35: 1.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different with the specific embodiment one or two is: in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 20～30: 1.Other is identical with the specific embodiment one or two.
The specific embodiment five: what present embodiment was different with the specific embodiment one or two is: in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 25: 1.Other is identical with the specific embodiment one or two.
The specific embodiment six: the preparation method of present embodiment nanometer cobalt ion-doped titanic anhydride catalyst is undertaken by following step: in the time of one, with 200～250r/min speed magnetic agitation butyl titanate is splashed in the absolute ethyl alcohol, butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the time that drips butyl titanate is 12～15min, dropwises the back and continues to stir; Two, drip concentrated hydrochloric acid (making inhibitor) in the reactant liquor of first butyl titanate drippage back 60min after step 1 is handled, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, the time that drips concentrated hydrochloric acid is 1～2min, add cobalt chloride subsequently, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, continue to stir; Three, drip distilled water (making gelatinizing agent) in the reactant liquor after step 2 is handled behind first butyl titanate drippage 90min, the volume ratio of distilled water and Butyl Phthalate is 5: 6, dripping the distilled water time is 12～15min, dropwises and obtains gel, again with the static ageing 0.5～2h of gel; Four, the gel after the ageing is put into baking oven, dry 3h under 100～105 ℃ condition becomes nanometer grade powder again after grinding; Five, nanometer grade powder is put into muffle furnace, be warming up to 500 ℃ with 2 ℃/min speed, knot 2h reburns; Promptly obtain the nanometre grade cobalt doping titanium dioxide catalyst.
The described nanometer cobalt ion-doped titanic anhydride catalyst of present embodiment is mainly used in the catalytic ozonation Drinking Water, can adopt existing catalytic ozonation method to handle, catalyst adopts disposable dosing method in the aforementioned catalytic ozonation method, ozone adds continuously, its process conditions: the ozone flux is 7mg/min, and the dosage of catalyst is 0.1mg/L.Under the same conditions, present embodiment TOC of yielding water clearance has improved more than 27.4% than ozone oxidation method, compares TiO
2The catalytic ozonation method has improved more than 22%.And the catalyst applied range of present embodiment can the catalytic ozonation removal be drunk the underwater trace persistent organic pollutants in pH value=2～12 scopes.
The specific embodiment seven: what present embodiment and the specific embodiment three were different is: the mass fraction of concentrated hydrochloric acid described in the step 2 is 36.5%.Other step and parameter are identical with the specific embodiment three.
The specific embodiment eight: what present embodiment was different with the specific embodiment one or two is: in the step 2 in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 15～35: 1.Other is identical with the specific embodiment one or two.
The specific embodiment nine: what present embodiment was different with the specific embodiment one or two is: in the step 2 in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 20～30: 1.Other is identical with the specific embodiment one or two.
The specific embodiment ten: what present embodiment was different with the specific embodiment one or two is: in the step 2 in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 25: 1.Other is identical with the specific embodiment one or two.
The specific embodiment 11: the preparation method of present embodiment nanometer cobalt ion-doped titanic anhydride catalyst be by following step carry out one, butyl titanate is splashed in the absolute ethyl alcohol with 200～250r/min speed magnetic agitation the time, butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the time that drips butyl titanate is 15min, dropwises the back and continues to stir; Two, dripping mass fraction in the reactant liquor of first butyl titanate drippage back 60min after step 1 is handled is 36.5% concentrated hydrochloric acid (making inhibitor), the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, the time that drips concentrated hydrochloric acid is 2min, add cobalt chloride subsequently, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 30: 1, continue to stir; Three, drip distilled water (making gelatinizing agent) in the reactant liquor after step 2 is handled behind first butyl titanate drippage 90min, the volume ratio of distilled water and Butyl Phthalate is 5: 6, dripping the distilled water time is 15min, dropwises and obtains gel, again with the static ageing 1h of gel; Four, the gel after the ageing is put into baking oven, dry 3h under 100 ℃ condition becomes nanometer grade powder again after grinding; Five, nanometer grade powder is put into muffle furnace, be warming up to 500 ℃ with 2 ℃/min speed, knot 2h reburns; Promptly obtain the nanometre grade cobalt doping titanium dioxide catalyst.
With following experiment is the effect of example checking present embodiment:
Experiment one: adopt ozone oxidation method, TiO respectively
2Catalytic ozonation method and Co
X+Doped Ti O
2Catalytic ozonation method p-nitrophenyl initial concentration is that the 3.075mg/L and the water yield are the nitrobenzene sewage disposal 20min of 1L; Above-mentioned three kinds of method ozone and oxygen all adopt continuous dosing method, and the ozone flux is 7mg/min; TiO
2Catalytic ozonation method, Co
X+Doped Ti O
2Catalyst adopts disposable dosing method described in the catalytic ozonation method, and catalyst amounts is 0.1g/L, Co
X+Doped Ti O
2Catalyst described in the catalytic ozonation method is to adopt the preparation of present embodiment method; Experimental result as shown in Figure 1.
As shown in Figure 1, under the same reaction conditions, the catalyst of present embodiment preparation is to the TOC of yielding water clearance, with TiO
2The catalytic ozonation method is compared and has been improved 22.0%, compares with the ozone oxidation method and has improved 27.4%.
Experiment two: adopt ozone oxidation method, TiO respectively
2Catalytic ozonation method and Co
X+Doped Ti O
2Catalytic ozonation method p-nitrophenyl initial concentration is that the 60.2 μ g/L and the water yield are the nitrobenzene sewage disposal 20min of 1L; Above-mentioned three kinds of method ozone all adopt disposable dosing method, and ozone concentration is 0.3mg/L, TiO
2Catalytic ozonation method, Co
X+Doped Ti O
2Catalyst adopts disposable dosing method described in the catalytic ozonation method, and catalyst amounts is 0.1g/L, Co
X+Doped Ti O
2Catalyst described in the catalytic ozonation method is to adopt the preparation of present embodiment method; Experimental result as shown in Figure 2.
As shown in Figure 2, under same reaction conditions, the clearance of the catalyst p-nitrophenyl of present embodiment preparation is compared with the ozone oxidation method and has been improved 40.04%, TiO
2The catalytic ozonation method is compared with the ozone oxidation method and has been improved 40.81%; As seen, add the removal characteristic that cobalt ions does not change p-nitrophenyl.
Adopt the method for experiment one, utilize the catalyst of present embodiment preparation pH value to be respectively 2,4,6,7,8,9 and 12 nitrobenzene initial concentration and be 3.075mg/L and the water yield nitrobenzene sewage disposal 20min, its step and parameter and test one identical for 1L; The clearance of TOC of yielding water clearance and nitrobenzene is basic identical, and the difference of the TOC of yielding water clearance of different pH value nitrobenzene sewage and the clearance of nitrobenzene is in ± 0.05%.
Claims (10)
1, nanometer cobalt ion-doped titanic anhydride catalyst, it is characterized in that nanometer cobalt ion-doped titanic anhydride catalyst is to be made by butyl titanate, absolute ethyl alcohol, cobalt chloride, concentrated hydrochloric acid and distilled water, wherein butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, the volume ratio of distilled water and Butyl Phthalate is 5: 6.
2, nanometer cobalt ion-doped titanic anhydride catalyst according to claim 1, the mass fraction that it is characterized in that described concentrated hydrochloric acid is 36.5%.
3, nanometer cobalt ion-doped titanic anhydride catalyst according to claim 1 and 2 is characterized in that in the butyl titanate that the mol ratio of Co element is 15～35: 1 in the Ti element and cobalt chloride.
4, nanometer cobalt ion-doped titanic anhydride catalyst according to claim 1 and 2 is characterized in that in the butyl titanate that the mol ratio of Co element is 20～30: 1 in the Ti element and cobalt chloride.
5, nanometer cobalt ion-doped titanic anhydride catalyst according to claim 1 and 2 is characterized in that in the butyl titanate that the mol ratio of Co element is 25: 1 in the Ti element and cobalt chloride.
6, the preparation method of nanometer cobalt ion-doped titanic anhydride catalyst according to claim 1, the preparation method who it is characterized in that nanometer cobalt ion-doped titanic anhydride catalyst is undertaken by following step: in the time of one, with 200～250r/min speed magnetic agitation butyl titanate is splashed in the absolute ethyl alcohol, butyl titanate and absolute ethyl alcohol volume ratio are 1: 4, the time that drips butyl titanate is 12～15min, dropwises the back and continues to stir; Two, drip concentrated hydrochloric acid in the reactant liquor of first butyl titanate drippage back 60min after step 1 is handled, the volume ratio of Butyl Phthalate and concentrated hydrochloric acid is 12: 1, the time that drips concentrated hydrochloric acid is 1～2min, add cobalt chloride subsequently, in the butyl titanate in Ti element and the cobalt chloride mol ratio of Co element be 10～40: 1, continue to stir; Three, drip distilled water in the reactant liquor after step 2 is handled behind first butyl titanate drippage 90min, the volume ratio of distilled water and Butyl Phthalate is 5: 6, dripping the distilled water time is 12～15min, dropwises and obtains gel, again with the static ageing 0.5～2h of gel; Four, the gel after the ageing is put into baking oven, dry 3h under 100～105 ℃ condition becomes nanometer grade powder again after grinding; Five, nanometer grade powder is put into muffle furnace, be warming up to 500 ℃ with 2 ℃/min speed, knot 2h reburns; Promptly obtain the nanometre grade cobalt doping titanium dioxide catalyst.
7, the preparation method of nanometer cobalt ion-doped titanic anhydride catalyst according to claim 6, the mass fraction that it is characterized in that concentrated hydrochloric acid described in the step 2 is 36.5%.
8,, it is characterized in that in the step 2 in the butyl titanate that the mol ratio of Co element is 15～35: 1 in the Ti element and cobalt chloride according to the preparation method of claim 6 or 7 described nanometer cobalt ion-doped titanic anhydride catalysts.
9,, it is characterized in that in the step 2 in the butyl titanate that the mol ratio of Co element is 20～30: 1 in the Ti element and cobalt chloride according to the preparation method of claim 6 or 7 described nanometer cobalt ion-doped titanic anhydride catalysts.
10,, it is characterized in that in the step 2 in the butyl titanate that the mol ratio of Co element is 25: 1 in the Ti element and cobalt chloride according to the preparation method of claim 6 or 7 described nanometer cobalt ion-doped titanic anhydride catalysts.
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| CN101859906A (en) * | 2010-06-07 | 2010-10-13 | 重庆大学 | Non-noble metal fuel cell oxygen reduction electrocatalyst |
| CN102008961A (en) * | 2010-11-26 | 2011-04-13 | 西安理工大学 | Method for chemical synthesis of mixed crystal type cobalt-doped titanium dioxide nanocrystalline |
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| CN101859906A (en) * | 2010-06-07 | 2010-10-13 | 重庆大学 | Non-noble metal fuel cell oxygen reduction electrocatalyst |
| CN101859906B (en) * | 2010-06-07 | 2012-06-06 | 重庆大学 | Non-noble metal fuel cell oxygen reduction electrocatalyst |
| CN102008961A (en) * | 2010-11-26 | 2011-04-13 | 西安理工大学 | Method for chemical synthesis of mixed crystal type cobalt-doped titanium dioxide nanocrystalline |
| CN102583636A (en) * | 2012-01-12 | 2012-07-18 | 重庆文理学院 | Nanometer cobalt-doped titanium dioxide/chitosan composite microspheres for photolyzing organophosphorus pesticide wastewater |
| CN102583636B (en) * | 2012-01-12 | 2015-10-28 | 重庆文理学院 | Mixed nanometer cobalt titanium dioxide/chitosan compound microsphere photodissociation organophosphorus pesticide wastewater |
| CN105413690A (en) * | 2015-10-26 | 2016-03-23 | 湖南永清环保研究院有限责任公司 | Catalyst for degrading organic wastewater and preparation method thereof |
| CN105703031A (en) * | 2016-03-21 | 2016-06-22 | 上海交通大学 | Method for preparing doped type photocatalytic material from negative electrode waste material of lithium titanate battery |
| CN105703031B (en) * | 2016-03-21 | 2018-10-23 | 上海交通大学 | The method for preparing doping type catalysis material using negative electrode of lithium titanate battery waste material |
| CN108314214A (en) * | 2018-02-26 | 2018-07-24 | 彭波涛 | A kind of technique of heterogeneous ozone catalytic degradation dyeing waste water |
| CN108358299A (en) * | 2018-02-26 | 2018-08-03 | 彭波涛 | A kind for the treatment of process of ozone catalytic degradation of dye waste water |
| CN108314214B (en) * | 2018-02-26 | 2020-07-28 | 广西研创企业管理咨询有限公司 | Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis |
| CN109603830A (en) * | 2018-12-12 | 2019-04-12 | 黑龙江科技大学 | A kind of preparation method of titanium-based composite nano materials film |
| CN109440158A (en) * | 2018-12-28 | 2019-03-08 | 南京时恒电子科技有限公司 | A kind of Cu-Ti-Co combination electrode and preparation method thereof |
| CN110665508A (en) * | 2019-10-08 | 2020-01-10 | 攀枝花学院 | Cobalt-doped high-titanium blast furnace slag photocatalytic material and application thereof |
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