CN111437804A - Method for preparing ozone oxidation catalyst by using titanium sludge - Google Patents

Method for preparing ozone oxidation catalyst by using titanium sludge Download PDF

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CN111437804A
CN111437804A CN202010291086.3A CN202010291086A CN111437804A CN 111437804 A CN111437804 A CN 111437804A CN 202010291086 A CN202010291086 A CN 202010291086A CN 111437804 A CN111437804 A CN 111437804A
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titanium
sludge
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oxidation catalyst
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马鲁铭
林晓姿
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Tongji University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/11—Turbidity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/20—Total organic carbon [TOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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Abstract

The invention relates to a method for preparing an ozone oxidation catalyst by using titanium sludge, which comprises the following steps: (1) drying: drying the titanium mud for 12-36 h at 60-100 ℃, and controlling the water content to be less than 20%; (2) crushing: crushing the dried titanium mud into particles with the diameter of 5-25 mm; (3) oxidizing and roasting: placing titanium mud particles in a muffle furnace, controlling the temperature to be 200-900 ℃, roasting for 50-300 min, and controlling the oxygen content in the furnace to be 15-25%; (4) cooling and cleaning: and (4) after roasting, cooling and cleaning residual loose mud and ash on the surface. Compared with the prior art, the method has the advantages of high resource utilization rate, good catalytic ozonation effect and the like.

Description

Method for preparing ozone oxidation catalyst by using titanium sludge
Technical Field
The invention belongs to the field of water pollution control, and particularly relates to a method for preparing an ozone oxidation catalyst by using titanium sludge.
Background
China is rich in titanium resources, taking the Panxi area as an example, the reserve capacity of 8.7 hundred million tons has been proved, so that the titanium industry is developed vigorously, such as the production of titanium dioxide, titanium alloy plates and the like, and the waste titanium mud generated by the method is not ignored. For example, acidic waste water generated in pickling titanium plates is neutralized to form a large amount of precipitates, and the precipitates are subjected to filter pressing treatment to obtain the titanium sludge. The basic components of the titanium mud are various hydroxides and oxides of titanium, and the titanium mud has important recycling value. Because the enterprises lack of technical means, titanium mud is basically discarded as waste materials, which not only brings secondary pollution, but also wastes metal resources.
At present, aiming at the resource recycling of titanium mud, some application cases exist: for example, patent publication No. CN 104817147B discloses a method for preparing a polymeric silicon-calcium-iron coagulant for water treatment from titanium sludge, which uses industrial-grade sodium hydroxide, hydrochloric acid, sulfuric acid, sodium chlorate and sodium chlorate as auxiliary raw materials, and performs three-stage leaching reaction on titanium sludge by using different acids and alkalis to obtain the polymeric silicon-calcium-iron coagulant for water treatment, which can be applied to the fields of municipal sewage, industrial wastewater, seriously eutrophicated lake water and the like, and is particularly suitable for removing the chromaticity and organic matters of sewage. Although part of titanium resources can be recovered by the method, the recovery rate is not high, and secondary pollution is caused by using different acids and bases for many times.
Patent publication No. CN 102086491B discloses a method for recovering iron and titanium resources from titanium sludge, which mainly comprises the steps of drying and crushing the titanium sludge, adding coal powder and a binder, pressing, heating, reducing, and separating iron slag: and carrying out slag-iron separation on the red hot metalized pellets, wherein iron elements in the metalized pellets form molten iron for the next process, and titanium elements form high-titanium slag. The method can fully utilize iron and titanium resources with higher value in the titanium sludge, but has complex process, needs to additionally add a large amount of coal powder and adhesive, and has high recycling cost.
The patent publication No. CN 109847768A discloses the preparation of nano TiO by utilizing the molten slag of a titanium-containing electric furnace2/Mg2The method of using-xCaxFeCl composite material as photocatalyst adopts titaniferous electric furnace molten slag as raw material to synthesize TiO2/L DH composite material, product TiO obtained2the/L DH composite material can be used as catalyst and catalyst carrier in the fields of chemistry and chemical industry, as infrared and ultraviolet absorption and barrier material in the field of functional materials, as antibacterial additive, flame retardant and PVC stabilizer in the plastic industry, and has strong adsorption effect on a plurality of toxic and harmful ions in the field of environmental protection, thereby being used for purifying waterThe method has wide application prospect, but has complex steps, different temperatures, proportions of ions with different valence states and pH values of solution need to be carefully regulated and controlled in the process of preparing L DH, and the process conditions are not easy to control.
Although the methods recycle the titanium sludge resources and can also be used for sewage treatment, the methods have the problems of low recovery rate, complex process, difficult control of process conditions, additional pollution in the recovery process and the like. Until now, no research on recycling and processing titanium sludge into a catalytic ozone catalyst has been reported, the catalytic ozone oxidation is an important advanced oxidation technology and has important significance on upgrading and modifying refractory industrial wastewater, but the existing titanium sludge has some organic impurities on the surface, is dispersible particles, can be directly put into water without treatment, can easily decompose solids to generate colloid, causes turbidity, and has high difficulty in subsequent catalyst separation.
Disclosure of Invention
The present invention aims at providing one kind of process of preparing ozone oxidizing catalyst with titanium mud. Through removing surface impurities and re-granulating, the content of effective catalytic components in the titanium mud is improved, and meanwhile, titanium mud clusters are bonded into hard materials with uneven surfaces and prismatic or cylindrical particles, so that the reaction specific surface area is improved, and the loss of the titanium mud caused by decomposition in water is reduced.
The idea of the invention is as follows: (1) by roasting, the titanium-containing substances in the titanium sludge are ensured to be completely converted into TiO with catalytic activity to the maximum extent2A crystal; (2) adjusting TiO in titanium mud by optimizing preparation process parameters2Crystal form to improve the overall mechanical strength and wear resistance; on the premise of ensuring the catalytic effect, the loss of the catalyst in the water treatment process is reduced.
The purpose of the invention can be realized by the following technical scheme: the method for preparing the catalytic ozone catalyst for water treatment by resource utilization of titanium sludge comprises the following specific steps:
(1) selecting titanium mud subjected to filter pressing treatment, and primarily drying;
and (3) drying: the titanium mud is spread flatly (the height is about 10-20 mm), placed in a drying oven, and dried for 12-36 h (preferably 24h) at the set temperature of 60-100 ℃ (preferably 80 ℃), and the water content is controlled to be less than 20%. The step can reduce the volume of titanium mud and is beneficial to subsequent treatment.
(2) Crushing the preliminarily dried titanium mud;
the crushing: and putting the dried titanium mud into a ball mill, crushing the titanium mud into particles, wherein the diameter of the crushed particles is 5-25 mm (preferably 10-20 mm), and facilitating subsequent treatment. The specific surface area of the crushed particles is increased, and the contact area of the titanium mud is increased.
(3) Oxidizing and roasting the crushed titanium mud, and then naturally cooling;
and (3) oxidizing and roasting: the titanium sludge is placed in a muffle furnace, the temperature is controlled to be 200-900 ℃ (preferably 600-800 ℃), the roasting time is 50-300 min (preferably 100-200 min), and the oxygen content in the furnace is 15-25%.
The purpose of oxidizing roasting is as follows: (1) organic substances attached to the titanium sludge are removed through high-temperature oxidation, so that secondary pollution in use is avoided; (2) titanium hydroxide (Ti (OH)) in titanium sludge3) Oxidation to TiO2And by changing the TiO temperature2A crystalline form of (a); (3) the titanium mud is sintered into a material with prismatic or cylindrical particles on the surface at high temperature, so that the mechanical strength is improved, and the titanium mud can become a practical catalyst filler;
and (3) naturally cooling: after the roasting is finished, taking out the furnace after the temperature of the furnace is reduced to 150 ℃ and further cooling the furnace in the air.
The oxygen content of the furnace is controlled by adjusting the flow ratio of the oxygen and the nitrogen which are introduced into the muffle furnace. If the oxygen content in the roasting atmosphere is too low, the titanium-containing substances in the titanium sludge are not completely oxidized, the effective components are less, and the catalytic effect is poor. If the oxygen content is too high, the resource is wasted.
The temperature rise rate of the muffle furnace is 20 ℃/min.
(4) Cleaning the cooled titanium mud;
the cleaning: and (4) flushing for three times by using tap water to clean residual loose mud and ash on the surface.
The invention utilizes the titanium sludge which is a production waste, and the method comprises the following stepsSimple process for removing impurities and granulating to improve TiO in titanium mud2The content of the titanium mud enables the titanium mud small particles to be bonded and consolidated with each other, the surface of the titanium mud is in a rugged shape, the specific surface area is improved, the titanium mud loss caused by decomposition is reduced, the titanium mud can be directly used as a fixed bed filler, the method is a feasible way for reducing the cost of the catalytic ozone catalyst and reducing the pollution of production waste, and has important practical value.
The catalyst prepared by the method is used for catalyzing ozone to treat wastewater, the titanium mud catalyst is placed in a fixed bed reactor and is placed in the wastewater to be treated, ozone is simultaneously input into the wastewater, the adding amount of the catalyst is 15-25 g/L, the adding amount of the ozone is 25-35 mg/min, the treatment time is 2 hours, the catalytic ozone oxidation reaction is carried out, the TOC removal rate can reach 80%, and titanium dioxide (TiO) (the TOC removal rate can reach 80%)2) It is a transition metal oxide, and can form high-density surface hydroxyl on a solid-liquid interface in water. The research finds that the TiO2The surface hydroxyl group (2) can be bonded to ozone, and has catalytic ozone activity to decompose ozone and generate OH.
Compared with the prior art, the invention has the following advantages:
(1) the main components of the titanium mud are hydroxide, oxide and organic impurities, and after the titanium mud is treated by the method, the hydroxide is converted into TiO2Organic impurities are fully oxidized into carbon dioxide and water, and the catalytic active ingredient TiO is improved2To convert titanium sludge into a catalyst having a high catalytic ozone activity;
(2) the existing titanium mud is dispersible particles and has low mechanical strength. Consolidation by calcination to form TiO2Recrystallization and polycrystalline growth, and has certain mechanical strength and wear resistance, and the mechanical strength is 35-65N/cm2The specific surface area is 250 to 350m2(ii)/g, a packed catalyst having high mechanical strength; the existing titanium mud is dispersible particles after being dried, and has low mechanical strength. The invention improves the mechanical strength and the wear resistance through roasting and consolidation, and can be used as a filler type catalyst.
(3) The catalyst is roasted at high temperature, so that the components are stable, the prepared catalyst is tightly agglomerated and bonded in the interior, does not run off along with effluent, can be used for a long time, can be generally used for 3-5 years, and the catalytic activity can be maintained above 60%;
(4) the preparation method is green and environment-friendly, and no waste gas, waste water or waste residue is generated in the preparation process; the production waste is recycled, so that the secondary pollution is reduced;
(5) the cost is low, the main raw material titanium mud belongs to production waste, and no additional raw material is needed.
Drawings
FIG. 1 shows the surface states of titanium sludge after drying (left) and roasting (right), the surface is dark yellow after drying, the hardness is low, the surface is bright yellow after crushing and high-temperature roasting, and the mechanical strength is high;
FIG. 2 is an XRD pattern of the baked titanium paste in which the active ingredient is primarily titanium dioxide in the anatase form;
figure 3400 ℃ roasted titanium paste XRD pattern in which the active ingredient is predominantly anatase titanium dioxide;
FIG. 4800 ℃ roasted titanium sludge XRD pattern in which the active ingredient is mainly rutile titanium dioxide;
FIG. 5 shows the degradation effect of ozone alone and the catalytic ozone added with the prepared titanium sludge (roasted at 800 ℃) on simulated wastewater;
FIG. 6 shows the removal effect of adsorption on organic substances, which proves that the organic substances are mineralized only in the process of catalyzing ozone.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention.
The following examples prepare titanium catalysts based on different conditions and examine their stability in catalyzing ozone treatment of wastewater.
Example 1:
the method for preparing the catalytic ozone catalyst for water treatment by resource utilization of titanium sludge comprises the following specific steps:
(1) selecting titanium mud subjected to filter pressing treatment, and primarily drying;
and (3) drying: flatly spreading titanium mud (the height is about 10-20 mm), placing the titanium mud in a drying oven, setting the temperature to be 60-100 ℃, drying for 12-36 h, and controlling the water content to be less than 20%;
(2) crushing the preliminarily dried titanium mud;
the crushing: and putting the dried titanium mud into a ball mill, and crushing the titanium mud into particles, wherein the diameter of the crushed particles is 5-25 mm, so that the subsequent treatment is facilitated.
(3) Oxidizing and roasting the crushed titanium mud, and then naturally cooling;
and (3) oxidizing and roasting: and (3) placing the titanium mud in a muffle furnace, controlling the temperature to be 200-900 ℃, roasting for 50-300 min, and controlling the oxygen content in the furnace to be 15-25%.
And (3) naturally cooling: after the roasting is finished, taking out the furnace after the temperature of the furnace is reduced to 150 ℃ and further cooling the furnace in the air.
The oxygen content of the furnace is controlled by adjusting the flow ratio of the oxygen and the nitrogen which are introduced into the muffle furnace.
The temperature rise rate of the muffle furnace is 20 ℃/min.
(4) Cleaning the cooled titanium mud;
the cleaning: and (4) flushing for three times by using tap water to clean residual loose mud and ash on the surface.
Different phases of titanium mud are obtained by adjusting parameters of the preparation process, and a catalytic ozone oxidation experiment is carried out by the following method, wherein the experimental steps are as follows:
(a) titanium sludge is put into a fixed bed reactor for a catalytic ozone oxidation experiment, wherein a water sample is simulated wastewater, and the water quality indexes are that TOC is 60 mg/L, nitrate nitrogen is 30 mg/L and Cl -20 mg/L, 3 mg/L TP, 7.2 pH, 80mm diameter of reactor, 550mm height, 1.5L effective volume, 30g titanium catalyst dosage, 0.5L waste water, 30mg/min ozone dosage and 2h treatment time.
(b) The physicochemical properties of the prepared catalyst are considered: surface composition, mechanical strength, specific surface area; and treating the effluent quality: TOC, turbidity, total titanium content in water.
(c) Control experiment: titanium mud is not added, and the simulated wastewater is treated only by ozone. Adding amount of ozone: 30 mg/min; treatment time: and 2 h.
TABLE 1 influence of different crushed particle sizes of the examples
Figure BDA0002450415010000051
TABLE 2 influence of different calcination temperatures of the examples
Figure BDA0002450415010000061
TABLE 3 influence of different firing times of the examples
Figure BDA0002450415010000062
TABLE 4 influence of different oxygen contents of the examples
Figure BDA0002450415010000063
The results of the examples are given in the following table:
TABLE 6 effects of treatment of examples
Figure BDA0002450415010000064
Figure BDA0002450415010000071
(1) Influencing factor
Influence of crushed particle size: the crushing particle size is too small, the internal structure is tighter after roasting, the contact area of the catalyst and ozone is reduced, and the catalytic effect is influenced. If the crushed particle size is too large, the contact area with oxygen in the roasting process is reduced, and the roasting is not uniform. The above results show that the treatment effect is best when the crushed particle size is 15 mm.
Effect of temperature ① Effect on active ingredients: the titanium dioxide crystal grains grow by roasting, the crystal grain defects and the intercrystalline disordered structure are reduced, and the crystallization degree is improved. Simultaneously, the crystal structure is changed, and when the roasting temperature is below 600 ℃, the main component is anatase type TiO2At a calcination temperature of more than 600 ℃, the main component is rutile type TiO2② (see attached figures 2-4) influence on mechanical strength, i.e. the roasting temperature is too low, the internal consolidation degree is limited, the surface mechanical strength is low, the titanium dioxide catalyst is easy to fall off when being used as a catalyst, and the effluent turbidity and the total titanium content in water are influenced.
Influence of calcination time: the roasting time is too short, the titanium-containing substances in the titanium sludge are not completely oxidized, the effective components are few, the agglomeration degree is low, and the catalytic effect is poor, the effluent turbidity is high, and the total titanium content is high. The roasting time is too long, the energy is wasted, and meanwhile, the internal structure of the titanium mud is too compact, so that the number of active sites is reduced. The results show that the treatment effect is best when the roasting time is 150 min.
Influence of oxygen content: the oxygen content is too low, the titanium-containing substances in the titanium sludge are not completely oxidized, the effective components are less, and the catalytic effect is poor. The oxygen content is too high, which causes resource waste. The above results show that the treatment effect is best when the oxygen content is 20%.
(2) Water sample treatment effect
No catalyst is added, and the TOC removal effect is only 40%. After the prepared titanium mud catalyst is added, the TOC removal efficiency is greatly improved, and the final removal rate reaches 80% (see attached figure 5). The catalyst is added, ozone is not added, the TOC of the wastewater is hardly removed, and the influence of adsorption on the removal effect of the TOC is eliminated (see figure 6). The turbidity of the effluent and the total titanium concentration of the titanium catalyst prepared under the optimal condition in the using process are obviously lower than those of the control example which is not roasted. The prepared catalyst has high catalytic ozone activity and practical application value.
The titanium sludge also had a certain catalytic activity without calcination (comparative example). However, because of low surface strength, titanium sludge particles are easy to fall off, and effluent water flows out along with the falling of the effluent water, so that effluent water turbidity is caused, and the loss of the catalyst is caused due to the excessive total titanium concentration. The roasting measure of the invention solves the problem.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.

Claims (10)

1. A method for preparing an ozone oxidation catalyst by using titanium sludge is characterized by comprising the following steps:
(1) drying by baking
Drying the titanium mud for 12-36 h at 60-100 ℃, and controlling the water content to be less than 20%;
(2) crushing
Crushing the dried titanium mud into particles with the diameter of 5-25 mm;
(3) oxidizing roasting
Placing titanium mud particles in a muffle furnace, controlling the temperature to be 200-900 ℃, roasting for 50-300 min, and controlling the oxygen content in the furnace to be 15-25%;
(4) cooling and cleaning
And (4) after roasting, cooling and cleaning residual loose mud and ash on the surface.
2. The method for preparing the ozone oxidation catalyst by using the titanium sludge as claimed in claim 1, wherein the titanium sludge in the step (1) is spread in an oven for drying, and the spreading height of the titanium sludge is 10-20 mm.
3. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the titanium sludge in the step (2) is crushed in a ball mill.
4. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the particle size of the crushed titanium sludge in the step (2) is preferably 10-20 mm.
5. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the calcination temperature in the step (3) is preferably 600-800 ℃.
6. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the calcination time in step (3) is preferably 100-200 min.
7. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the oxygen content of the furnace in the step (3) is controlled by adjusting the flow ratio of oxygen and nitrogen introduced into the muffle furnace, and the oxygen content is preferably 18-21%.
8. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the temperature rise rate of the muffle furnace in the step (3) is 20 ℃/min.
9. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the cooling in the step (4) is performed by: and after the furnace temperature is reduced to 150 ℃, taking out the furnace and further cooling the furnace to room temperature in the air.
10. The method for preparing an ozone oxidation catalyst by using titanium sludge as claimed in claim 1, wherein the obtained catalyst has a mechanical strength of 35 to 65N/cm2The specific surface area is 250 to 350m2/g。
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