阅读说明：本技术 钴掺杂高钛型高炉渣光催化材料及其应用 (Cobalt-doped high-titanium blast furnace slag photocatalytic material and application thereof ) 是由 霍红英 邹敏 张欢欢 于 2019-10-08 设计创作，主要内容包括：本发明公开了一种钴掺杂高钛型高炉渣光催化材料及其应用,属于光催化领域。本发明光催化材料以高钛型高炉渣为原料制备得到：将高钛型高炉渣与水混合,加入乙酸,得溶液A；将Co(NO<Sub>3</Sub>)<Sub>2</Sub>·6H<Sub>2</Sub>O与水混合,得溶液B；将溶液B滴入溶液A中,调节体系pH至4～5,得悬浊液；悬浊液经干燥、研磨及煅烧,得钴掺杂高钛型高炉渣光催化材料。本发明通过采用液相法,以含钛高炉渣为原料,Co(NO<Sub>3</Sub>)<Sub>2</Sub>·6H<Sub>2</Sub>O为掺杂离子给体,制备Co掺杂含钛高炉渣的光催化剂,考察不同制备条件对催化剂晶体结构及大小的影响,用所制备的催化剂进行光催化分解有机物的研究,考察质量掺杂比、煅烧温度、煅烧时间等对光催化性能的影响。(The invention discloses a cobalt-doped high-titanium blast furnace slag photocatalytic material and application thereof, belonging to the field of photocatalysis. The photocatalytic material is prepared by taking high-titanium blast furnace slag as a raw material: mixing high titanium type blast furnace slag with water, and adding acetic acid to obtain a solution A; mixing Co (NO) 3 ) 2 ·6H 2 Mixing O with water to obtain solution B; dripping the solution B into the solution A, and adjusting the pH of the system to 4-5 to obtain a suspension; and drying, grinding and calcining the suspension to obtain the cobalt-doped high-titanium blast furnace slag photocatalytic material. The invention adopts a liquid phase method, takes the titanium-containing blast furnace slag as the raw material, and Co (NO) 3 ) 2 ·6H 2 O is a doped ion donor, a Co-doped titanium-containing blast furnace slag photocatalyst is prepared, the influence of different preparation conditions on the crystal structure and the size of the catalyst is inspected, the prepared catalyst is used for researching photocatalytic decomposition of organic matters, and the influence of mass doping ratio, calcination temperature, calcination time and the like on the photocatalytic performance is inspected.)

1. The cobalt-doped high titanium blast furnace slag photocatalytic material is characterized in that: the preparation method comprises the following steps:

A. uniformly mixing high titanium type blast furnace slag with water, and adding acetic acid while stirring to obtain a solution A;

B. mixing Co (NO)₃)₂·6H₂Mixing O and water uniformly to obtain solution B;

C. dripping the solution B into the solution A, adjusting the pH of the system to 4-5 after the dripping is finished, and then stirring vigorously in a water bath to obtain a suspension;

D. and drying the suspension, drying, grinding the dried solid, and calcining at the temperature of below 900 ℃ to obtain the cobalt-doped high-titanium blast furnace slag photocatalytic material.

2. The cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step A, the mass ratio of the high titanium blast furnace slag to water is 1: 4-1: 6.

3. the cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step A, the concentration of the acetic acid is 3-5 mol/L; the mass volume ratio of the high titanium type blast furnace slag to the acetic acid is 1: 0.5 to 0.8 g/mL.

4. The cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step C, after the dropwise addition is finished, controlling the mass ratio of Co to Ti in the system to be 0.01-0.05: 1.

5. the cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step C, nitric acid is adopted to adjust the pH value; the concentration of the nitric acid is 1-1.5 mol/L.

6. The cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step C, before water bath, the stirring speed is 30-40 r/min, and the time is 1-2 h; in the water bath, the speed of the violent stirring is 60-70 r/min, and the time is 2-2.5 h.

7. The cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in the step C, the temperature of the water bath is 58-62 ℃.

8. The cobalt-doped high titanium blast furnace slag photocatalytic material according to claim 1, characterized in that: in step D, at least one of the following is satisfied:

the drying temperature is 80-90 ℃, and the drying time is 11-13 h;

the calcining temperature is 600-900 ℃;

the calcining time is 1-5 h.

9. The cobalt-doped high titanium blast furnace slag photocatalytic material according to any one of claims 1 to 8, characterized in that: in the step D, the grinding is carried out to 30-60 um.

10. The application of the cobalt-doped high titanium blast furnace slag photocatalytic material as defined in any one of claims 1 to 9, wherein the application of the material comprises degradation of organic matters, treatment of sewage, sanitation and sterilization and air purification.

Technical Field

The invention belongs to the technical field of photocatalysis, and particularly relates to a cobalt-doped photocatalytic material taking high-titanium blast furnace slag as a raw material.

Background

TiO₂The photochemical catalyst has the advantages of stable photochemical property, no toxicity and good photocatalytic effect, so the photochemical catalyst is widely concerned. With pure TiO₂The TiO-based photocatalyst has been applied to many fields, and photocatalytic building materials, air purifiers, sewage treatment equipment and the like are all published, but pure TiO₂The cost of high volume applications is prohibitive.

The Panzhihua steel blast furnace slag is not only an industrial waste, but also a secondary resource rich in titanium. In recent decades, the utilization of high titanium blast furnace slag resources is mainly to extract titanium resources to prepare titanium-containing compounds and titanium-containing alloys. TiO in blast furnace slag₂The mass fraction is 20-23%, various elements are stable elements, and the photocatalytic degradation agent is completely possible to be used. However, the photocatalytic material prepared by directly utilizing the high titanium blast furnace slag has weak photocatalytic response and low photocatalytic degradation rate, and cannot meet the requirements of various application fields.

Disclosure of Invention

The invention aims to solve the technical problem of how to prepare a photocatalyst with excellent performance by using high-titanium blast furnace slag as a raw material.

The technical scheme adopted by the invention for solving the technical problem is to provide a cobalt-doped high-titanium blast furnace slag photocatalytic material, which is prepared by the following method:

A. uniformly mixing high titanium type blast furnace slag with water, and adding acetic acid while stirring to obtain a solution A;

B. mixing Co (NO)₃)₂·6H₂Mixing O and water uniformly to obtain solution B;

C. dripping the solution B into the solution A, adjusting the pH of the system to 4-5 after the dripping is finished, and then stirring vigorously in a water bath to obtain a suspension;

D. and drying the suspension, drying, grinding the dried solid, and calcining at the temperature of below 900 ℃ to obtain the cobalt-doped high-titanium blast furnace slag photocatalytic material.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step A, the mass ratio of the high titanium blast furnace slag to water is 1: 4-1: 6.

in the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step A, the concentration of acetic acid is 3-5 mol/L.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, the mass volume ratio of the high titanium blast furnace slag to acetic acid is 1: 0.5 to 0.8 g/mL.

In the step C, after the dropwise addition is finished, the mass ratio of Co to Ti in the system is controlled to be 0.01-0.05: 1.

in the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step C, nitric acid is adopted to adjust the pH value; the concentration of the nitric acid is 1-1.5 mol/L.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step C, before water bath, the stirring speed is 30-40 r/min, and the stirring time is 1-2 h.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, the violent stirring speed is 60-70 r/min and the time is 2-2.5 hours during water bath.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step C, the temperature of the water bath is 58-62 ℃.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the drying temperature is 80-90 ℃ and the drying time is 11-13 h.

Preferably, in the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the calcining temperature is 600-900 ℃.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the calcining time is 1-5 hours.

Preferably, in the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the calcining time is 2-5 hours.

More preferably, in the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the calcination time is 5 hours.

In the cobalt-doped high titanium blast furnace slag photocatalytic material, in the step D, the grinding is carried out to 30-60 um.

The invention also provides application of the cobalt-doped high titanium blast furnace slag photocatalytic material, which comprises the steps of degrading organic matters, treating sewage, cleaning and sterilizing, and purifying air.

The invention has the beneficial effects that:

the invention adopts a liquid phase method, takes the titanium-containing blast furnace slag as the raw material, and Co (NO)₃)₂·6H₂O is a doped ion donor, the Co-doped titanium-containing blast furnace slag photocatalyst is prepared, the influence of different preparation conditions on the crystal structure and size of the catalyst is inspected, the influence of mass doping ratio, calcination temperature, calcination time and the like on the photocatalytic performance is inspected, and the prepared photocatalytic material has excellent degradation capability.

Drawings

FIG. 1 is a flow chart of the preparation process of the cobalt-doped high titanium blast furnace slag photocatalytic material of the present invention.

FIG. 2 shows the effect of different Co mass doping ratios on the photocatalytic effect.

Figure 3 shows the degradation efficiency at different Co mass doping ratios.

Detailed Description

Specifically, the cobalt-doped high-titanium blast furnace slag photocatalytic material is prepared by the following method:

A. uniformly mixing high titanium type blast furnace slag with water, and adding acetic acid while stirring to obtain a solution A;

B. mixing Co (NO)₃)₂·6H₂Mixing O and water uniformly to obtain solution B;

C. dripping the solution B into the solution A, adjusting the pH of the system to 4-5 after the dripping is finished, and then stirring vigorously in a water bath to obtain a suspension;

D. and drying the suspension, drying, grinding the dried solid, and calcining at the temperature of below 900 ℃ to obtain the cobalt-doped high-titanium blast furnace slag photocatalytic material.

In order to ensure that the blast furnace slag can be uniformly and fully mixed with Co and the drying efficiency is accelerated in the subsequent reaction, in the step A, the mass ratio of the high-titanium blast furnace slag to water is 1: 4-1: 6.

the invention takes the blast furnace slag as the raw material, but the oxide in the blast furnace slag is hydrolyzed, if the oxide is hydrolyzed, the material structure in the blast furnace slag is changed, and the material structure is not a mixture containing the oxide, but a hydrolyzed alkaline substance, which does not have the photocatalysis condition. Therefore, the hydrolysis inhibitor is added in step A. The reason why the glacial acetic acid is adopted as the hydrolysis inhibitor is that the pH value can be properly adjusted while the hydrolysis is inhibited in the early stage; and glacial acetic acid can volatilize after heating, does not exert an influence on mixed liquor, can not mix other impurities into, does not influence the photocatalytic performance of sample.

In order to fully exert the hydrolysis inhibition function of acetic acid, control the pH of a system and fully inhibit the hydrolysis degree of titanium oxide, in the step A, the concentration of acetic acid is controlled to be 3-5 mol/L; the mass volume ratio of the high titanium type blast furnace slag to the acetic acid is 1: 0.5 to 0.8 g/mL.

In step B, Co (NO)₃)₂·6H₂The amount of O is measured by the cobalt-titanium mass ratio. Since the cobalt element is not volatilized, water is evaporated in the later drying and calcining processes, so that the reaction result is not greatly influenced by the water consumption in the step B. However, it should be noted that Co (NO)₃)₂·6H₂O is generally added into the solution A in a solution form, so that Co is fully mixed with the blast furnace slag, and local tissue unevenness is avoided.

Due to the multiple valence state of the transition metal element in TiO₂The doped small amount of transition metal ions can be used for capturing a photo-generated electron-hole pair shallow well, and the recombination time of electrons and holes is prolonged, so that the TiO content is improved₂Photocatalytic activity of (1). The research of the invention finds that the degradation rate of most transition metals for degrading organic matters after being doped can only be improved by 15 percent, but the degradation rate of cobalt-doped blast furnace slag can be improved by about 30 percent, so that the invention adopts the cobalt-doped high-titanium blast furnace slag to prepare the photocatalytic material and controls the systemThe mass ratio of the internal Co to the Ti is 0.01-0.05: 1.

in the step C, the solution B is dripped into the solution A, so that the addition amount of Co is convenient to control, and Co can be fully contacted and reacted with the blast furnace slag; if the solution A is added into the solution B dropwise, insoluble mixture in the solution A is easy to adhere to a beaker, so that the reaction is not uniform, and the performance of the photocatalytic material is influenced.

And in the step C, after the dropwise addition is finished, regulating the pH value by adopting 1-1.5 mol/L nitric acid to inhibit the hydrolysis reaction. After the pH value of the system is adjusted, the stirring time is controlled to be 1-2 h at the speed of 30-40 r/min, insoluble substances are gradually produced in the system, a uniform solid-liquid mixture is formed, then water bath is carried out at the temperature of 58-62 ℃, Co is further doped with blast furnace slag, water and acetic acid are gradually evaporated at the moment, the insoluble substances are increased, and therefore the stirring time is controlled to be 2-2.5 h at the speed of 60-70 r/min, and Co can be uniformly attached to the surface of the blast furnace slag.

In the step D, the suspension is dried for 11-13 h at the temperature of 80-90 ℃, the obtained dried substance has uneven surface substances, the substance with higher density is deposited at the bottom, and the substance with lower density is on the surface and cannot be effectively and uniformly mixed, so that the dried substance must be ground to 30-60 mu m and then calcined, otherwise the subsequent calcination affects the texture structure of the blast furnace slag.

Besides the great influence of the cobalt doping amount on the degradation efficiency of the photocatalytic material, the calcination temperature and the calcination time also have the influence, and through a screening test, the calcination temperature is controlled to be 600-900 ℃, the calcination time is 1-5 hours, and the degradation efficiency can reach more than 80%; the best calcining condition is calcining for 5 hours at 600 ℃.

The cobalt-doped high titanium blast furnace slag photocatalytic material provided by the invention can fully exert the photocatalytic performance of the blast furnace slag with extremely low economic cost because the components of the slag are not damaged for separation or extraction. The cobalt-doped high titanium blast furnace slag photocatalytic material can be directly used for producing ceramics or added into other materials, and can achieve the purposes of decomposing organic pollutants in water, purifying ambient air, sterilizing and removing peculiar smell.

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.