CN104276631B - A kind of iron scale basal granule sub-electrode and preparation method thereof - Google Patents

Abstract

The invention relates to an iron oxide sheet-based particle electrode for a three-dimensional electrode reactor and a preparation method thereof: it is composed of iron oxide sheet, shale, a pore-forming agent and an activator, and the dry fine iron sheet particle is 50-60% by weight percentage 10-20% dry fine shale, 10-20% pore-forming agent, and 10-20% activator. The present invention uses iron oxide scale as a raw material to prepare particle electrodes, opens up a new way for the application of iron oxide scale, realizes the maximum recycling of industrial waste, improves the comprehensive utilization level of iron oxide scale, and is beneficial to the sustainable development of my country's industry. It is of practical significance for our country to realize the "harmless, reduction, and recycling" of solid waste.

Description

A kind of iron oxide skin-based particle electrode and preparation method thereof

technical field

The invention belongs to the technical field of wastewater treatment, and in particular relates to an iron oxide skin-based particle electrode for treating refractory organic matter in urban sewage and a preparation method thereof.

Background technique

Iron oxide scale is formed by the reaction of steel and oxygen in the air during forging and hot rolling of steel. If these resources are used rationally, production costs can be reduced, and at the same time, environmental protection and energy saving can be played. The main components of iron oxide scale are Fe ₂ O ₃ , Fe ₃ O ₄ and FeO, and these oxides are precisely the activation-promoting components for particle electrode preparation. Therefore, using these available oxides in iron oxide scales to synthesize efficient and environmentally friendly particle electrodes for the treatment of urban sewage can make effective use of iron oxide scales, so as to achieve the purpose of "treating waste with waste" and obtain good economic benefits. .

Contents of the invention

The object of the present invention is to provide an iron oxide scale-based particle electrode and a preparation method thereof with the iron oxide scale as the substrate. The particle electrode material provided by the invention is used as a working electrode of a three-dimensional electrode reactor, can effectively degrade organic matter in waste water, and has high current efficiency and low energy consumption.

An iron oxide scale-based particle electrode, in terms of weight percentage, dry fine iron oxide scale particles account for 50-60%, dry fine shale accounts for 10-20%, pore-forming agent accounts for 10-20%, and activator accounts for 10-20% .

The pore-forming agent may be one of carbon powder, sawdust, starch, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and polystyrene particles.

The activator may be one of Fe ₃ O ₄ , Fe ₂ O _{3 ,} MnO ₂ , and ZnO.

The iron oxide scale is formed by the reaction of steel and oxygen in the air during steel forging and hot rolling, and its main components are Fe ₂ O ₃ , Fe ₃ O ₄ and FeO, which is a kind of industrial waste.

The preparation method of the above-mentioned iron oxide skin-based particle electrode comprises the following steps:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C. Mix and stir the dry fine iron scale particles in step A, dry fine shale in step B, pore-forming agent and activator according to a certain weight percentage, and extrude them into raw material balls;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw material balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 10-30min, Then heat it up to 1050°C at 300°C/h and bake for 10-30min, then cool down to room temperature naturally to obtain the iron oxide skin-based particle electrode material.

In terms of weight percentage, dry fine iron oxide scale particles account for 50-60%, dry fine shale accounts for 10-20%, pore forming agent accounts for 10-20%, and activator accounts for 10-20%.

The pore-forming agent may be one of carbon powder, sawdust, starch, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and polystyrene particles.

The activator may be one of Fe ₃ O ₄ , Fe ₂ O _{3 ,} MnO ₂ , and ZnO.

The iron oxide sheet-based particle electrode prepared by the above preparation method takes solid waste iron oxide sheet as a raw material. Iron oxide scale contains many kinds of oxides, among which the content of Fe ₂ O ₃ , Fe ₃ O ₄ and FeO is relatively high, and these oxides are precisely the components of activation promoters for the preparation of particle electrodes. Iron oxide skin-based particle electrode particles have a rough surface, which has a good adsorption and removal effect on pollutants in wastewater. Moreover, the stacking of iron oxide scales not only requires capital and a large area of stockpiles, but also pollutes the environment. Utilizing iron oxide sheets to make particle catalytic electrodes for three-dimensional electrodes can turn waste into treasure, reduce environmental pollution, and solve land occupation problems.

The iron oxide skin-based particle electrode and the preparation method thereof provided by the invention comply with the current national environmental protection policy of energy conservation and emission reduction. The prepared particle electrode is porous and has a large pore size, has a large specific surface area, strong adsorption performance, good conductivity and catalytic performance, and is a new type of high-efficiency particle electrode.

The present invention will be further described below in combination with specific embodiments.

detailed description

Embodiment one:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C, the dry fine iron scale particles in step A, the dry fine shale in step B, carbon powder and Fe ₃ O ₄ are mixed and stirred evenly according to the weight percentage of 50%:20%:20%:10%, Extruded into raw material balls;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reach 95%.

Embodiment two:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C, the dry fine iron scale particles in step A, the dry fine shale in step B, sawdust and Fe ₂ O ₃ are mixed and stirred evenly according to the weight percentage of 55%:15%:15%:15%, Extruded into raw material balls;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 94%.

Embodiment three:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C, the dry fine iron scale particles in step A, the dry fine shale in step B, starch and _MnO According to the percentage by weight of 60%: 15%: 15%: 10%, mix and stir, extrude into raw material ball;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 94%.

Embodiment four:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C, dry fine iron oxide scale particles in step A, dry fine shale in step B, starch and _MnO According to the percentage by weight of 60%: 10%: 10%: 20%, mix and stir, extrude into raw material ball;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 96%.

Embodiment five:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C. Mix and stir the dry fine iron scale particles in step A, the dry fine shale in step B, polyvinyl alcohol (PVA) and ZnO according to the weight percentage of 55%:15%:20%:10%. , extruded into raw material balls;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 96%.

Embodiment six:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C, the dry fine iron scale particles in step A, the dry fine shale in step B, polyvinyl butyral (PVB) and ZnO are mixed according to the weight percentage of 55%:15%:20%:10%. And stir evenly, extrude into raw material ball;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 97%.

Embodiment seven:

A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out (the purpose of washing and soaking is to desorb impurities), dried in an oven at 120°C, and then passed through a 60-mesh sieve to take dry fine iron oxide scale particles for later use;

B. Put the shale in an oven to dry at 120°C, crush the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale for later use;

C. Mix and stir the dry fine iron scale particles in step A, the dry fine shale in step B, polystyrene and ZnO according to the weight percentage of 55%:10%:15%:20%, and extrude into raw material balls;

D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours;

E. Put the raw meal balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 20 minutes, and then 300°C/h rising to 1050°C for 30min, then naturally cooling to room temperature to obtain the iron oxide skin-based particle electrode material.

Take 5.0 g of the iron oxide sheet-based particle electrode prepared in the above example, fill it in the reactor, and make a three-dimensional electrode reactor. When the voltage is 6.0V and the current is 0.2A, 30ml of printing and dyeing wastewater is degraded by electricity for 45min, and the removal rate of CODcr Reached 94%.

Claims (6)

1. An iron oxide skin-based particle electrode, characterized in that: according to weight percentage, it comprises dry fine iron oxide scale particles 50-60%, dry fine shale 10-20%, pore-forming agent 10-20%, and activator 10% -20%. 2. The iron oxide skin-based particle electrode as claimed in claim 1, characterized in that: the pore-forming agent is carbon powder, sawdust, starch, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyphenylene One of the vinyl granules. 3. The iron oxide sheet-based particle electrode according to claim 1, characterized in that the activator is one of Fe ₃ O ₄ , Fe ₂ O ₃ , MnO ₂ , and ZnO. 4. a preparation method of iron oxide skin-based particle electrode, is characterized in that, comprises the following steps: A. The iron oxide scale particles are ball milled in a ball mill, washed and soaked after being taken out, dried in an oven at 120°C, and then passed through a 60-mesh sieve to obtain dry fine iron oxide scale particles; B. Put the shale in an oven to dry at 120°C, pulverize the dried shale in a mortar, pass through a 60-mesh sieve, and take the dried fine shale; C. The dry fine iron scale particles in step A, the dry fine shale in step B, the pore-forming agent and the activator include 50-60% of dry fine iron scale particles and 10% of dry fine shale according to a certain weight percentage. -20%, pore forming agent 10-20%, activator 10-20%, mix and stir evenly, extrude into raw ball; D. Bake the raw meal balls in step C at 120°C in an oven for 24 hours; E. Put the raw material balls dried in step D in a high-temperature furnace from room temperature at 120°C/h to 300°C, heat for 2 hours, then rise at 60°C/h to 550°C, activate for 10-30min, Then heat it up to 1050°C at 300°C/h and bake for 10-30min, then cool down to room temperature naturally to obtain the iron oxide skin-based particle electrode material. 5. the preparation method of iron oxide scale base particle electrode as claimed in claim 4 is characterized in that: described pore forming agent is carbon powder, sawdust, starch, polyvinyl alcohol (PVA), polyvinyl butyral ( PVB), one of polystyrene particles. 6 . The method for preparing iron oxide scale-based particle electrodes according to claim 4 , wherein the activator is one of Fe ₃ O ₄ , Fe ₂ O ₃ , MnO ₂ , and ZnO.