阅读说明：本技术 一种钢铁冶金尘泥制备橡塑改性添加剂的工艺方法 (Process method for preparing rubber and plastic modified additive by using ferrous metallurgy dust and mud ) 是由 丁宝文 于 2019-11-14 设计创作，主要内容包括：本发明属于属于橡塑添加剂技术领域,尤其是一种钢铁冶金尘泥制备橡塑改性添加剂的工艺方法,该工艺方法方法简单,原料来源广泛,成本低,制备的反应过程操作简单易行,原料廉价易得,反应效率较高且重复性较好,并且对橡胶塑料具有良好的抗紫外线老化作用和耐磨作用,是对高炉瓦斯泥、烧结机头电除尘灰、炉前矿槽除尘灰的二次资源的充分利用,而且有利于环境保护,具有显著的经济价值和社会效益。(The invention belongs to the technical field of rubber and plastic additives, and particularly relates to a process method for preparing a rubber and plastic modified additive from ferrous metallurgy dust and sludge, which has the advantages of simple process, wide raw material source, low cost, simple and easy operation of the preparation reaction process, cheap and easily available raw materials, high reaction efficiency, good repeatability, good ultraviolet aging resistance and wear resistance on rubber and plastic, full utilization of secondary resources of blast furnace gas sludge, sintering machine head electric dedusting ash and furnace front ore tank dedusting ash, contribution to environmental protection and remarkable economic value and social benefit.)

1. A process method for preparing a rubber and plastic modified additive by using ferrous metallurgy dust and sludge is characterized by comprising the following steps:

(1) crushing, drying and grinding 20-25 parts of blast furnace gas mud, 10-13 parts of electric dedusting ash of a sintering machine head and 16-23 parts of dedusting ash of a stokehole ore tank, uniformly stirring, dispersing and mixing to obtain mixed treatment powder, enriching, leaching and mixing the mixed treatment powder for 0.5-1 h by adopting a saturated CO2 aqueous solution,

(2) adding a microbial bacterial liquid and a calcification liquid into the mixed treatment powder for treatment and induction to generate calcification load mixed treatment powder and a leachate, wherein the mixed treatment powder is formed by adding 80-100L of microbial bacterial liquid per ton and stacking, the microbe is bacillus pasteurianus ATCC11859, the calcification liquid is formed by mixing ammonium nitrate and calcium chloride, the final concentration of the ammonium nitrate is 0.1-0.15 mo1/L, the final concentration of the calcium chloride is 0.15-0.2 mol/L, the total using amount of the calcification liquid is 1-2 times of the using amount of the added bacterial liquid, and the bacterial concentration of the bacillus pasteurianus bacterial liquid is 1 × 10⁷~1×10⁹cfu/mL；

(3) Adding the calcification treatment powder into a sulfuric acid solution for acid leaching, performing solid-liquid separation on leached ore pulp to obtain filter residue and filtrate, adding a hydrogen peroxide solution and limestone into the filtrate for oxidation and neutralization iron precipitation, and filtering to obtain iron-containing slag and iron-removed liquid, wherein the iron-containing slag is used for recovering iron;

(4) under the condition that the temperature is 80 ℃, the iron-removed liquid obtained in the step (3) is mixed with the blast furnace gas mud and the zinc chloride according to the mass ratio of 30: 1.5-3.0, adding zinc chloride powder, stirring, reacting, precipitating for 1-2 h, and filtering to obtain calcium-magnesium slag and a zinc sulfate solution;

(5) and (4) sequentially adding the zinc sulfate solution obtained in the step (4) into an iron bicarbonate or ammonium carbonate solution for crystallization to precipitate zinc carbonate, filtering and washing, evaporating, concentrating, dehydrating, air-drying, transferring into a muffle furnace, and calcining to obtain the rubber and plastic modified additive.

2. The method for preparing the rubber and plastic modified additive from the ferrous metallurgy dust and sludge as claimed in claim 1, wherein the blast furnace gas sludge in the step (1) is crushed, dried and ground to obtain a powdery blast furnace gas sludge material with the particle size of 0.050 mm-0.07 mm.

3. The process method for preparing the rubber and plastic modified additive from the ferrous metallurgy dust and sludge according to claim 1, wherein the acid leaching process in the step (1) is specifically as follows: under the condition of 70 ℃, the powder with the powdery calcification treatment is prepared by mixing the following components in a solid-to-liquid ratio of 2: adding 5g/mL of the mixed solution into 0.5-0.8 mol/L of sulfuric acid solution for leaching for 5-8 min, standing and settling for 5-8 min after leaching is finished, and then carrying out solid-liquid separation to obtain filter residue and filtrate.

4. The process method for preparing the rubber and plastic modified additive from the ferrous metallurgy dust and sludge as claimed in claim 1, wherein the step (1) of oxidizing, neutralizing and depositing iron comprises the following specific steps: at room temperature, according to the ratio of the mass of the calcification treatment powder to the volume of the hydrogen peroxide solution being 30: 2-3 g/mL, adding 30wt% hydrogen peroxide solution into the filtrate, uniformly mixing, and then adding limestone to adjust the pH value to 5.2-5.4 to obtain iron-removed liquid and iron slag.

5. The process method for preparing the rubber and plastic modified additive from the ferrous metallurgy dust and mud as claimed in claim 1, wherein the zinc sulfate solution obtained in the step (5) is evaporated and concentrated to the supersaturation degree of 1.83g/ml, then the zinc sulfate solution is placed in ice water at the temperature of 0 ℃ for cooling and crystallization for 10-12 h to obtain water, and the high-purity water-containing zinc sulfate is prepared after dehydration and air drying.

Technical Field

The invention belongs to the technical field of rubber and plastic additives, and particularly relates to a process method for preparing a rubber and plastic modified additive from ferrous metallurgy dust and sludge.

Background

The blast furnace gas mud is fine sludge obtained by discharging blast furnace dry dust removal ash and coal gas washing sewage of an iron-making plant into a sedimentation tank and carrying out sedimentation treatment. The amount of blast furnace dust generated is generally 15 to 50 kg/t. The blast furnace gas mud has the main characteristics of high zinc content, high water content, high iron content, high carbon content and fine particle size, and zinc mainly exists in smaller particles. The zinc load is gradually increased due to the circulation and accumulation of zinc in the blast furnace, and a series of damages are generated to the blast furnace due to the over-high zinc load in the blast furnace. Many factories in China cannot be matched with the prior art of steel mills, so wet methods are not used or are rarely used for treating blast furnace dust containing zinc and lead. The pyrogenic process zinc recovery technology is characterized by that it utilizes the low boiling point of zinc, under the condition of high-temp. reduction the zinc oxide is reduced, and gasified into zinc vapour, and discharged together with flue gas so as to separate zinc from solid phase. In the gasification phase, the zinc vapour is again easily oxidised to form zinc oxide particles, which are collected together with the flue dust in the flue gas treatment system. The field needs to develop a novel process method for preparing the rubber and plastic modified additive by using the ferrous metallurgy dust and mud, and the application field of recycling the recyclable wastes of the electric dedusting ash of the head of the blast furnace gas mud sintering machine and the dedusting ash of the ore tank in front of the blast furnace is expanded.

Disclosure of Invention

Aiming at the problems, the invention aims to provide a process method for preparing the rubber and plastic modified additive by using the ferrous metallurgy dust and mud.

The invention is realized by the following technical scheme:

a process method for preparing a rubber and plastic modified additive by using ferrous metallurgy dust and sludge comprises the following specific steps:

(1) the method comprises the following steps of crushing, drying, grinding, uniformly stirring, dispersing and mixing 20-25 parts of TFe36.60 blast furnace gas mud, 10-13 parts of sintering machine head electro-precipitator dust and 16-23 parts of furnace front ore tank precipitator dust to obtain mixed treatment powder, and adopting saturated CO₂The aqueous solution is enriched, extracted and mixed to treat powder for 0.5 to 1 hour,

(2) adding a microbial bacterial liquid and a calcification liquid into the mixed treatment powder for treatment and induction to generate calcification load mixed treatment powder and a leachate, wherein the mixed treatment powder is formed by adding 80-100L of microbial bacterial liquid per ton and stacking, the microbe is bacillus pasteurianus ATCC11859, the calcification liquid is formed by mixing ammonium nitrate and calcium chloride, the final concentration of the ammonium nitrate is 0.1-0.15 mo1/L, the final concentration of the calcium chloride is 0.15-0.2 mol/L, the total using amount of the calcification liquid is 1-2 times of the using amount of the added bacterial liquid, and the bacterial concentration of the bacillus pasteurianus bacterial liquid is 1 × 10⁷~1×10⁹cfu/mL；

(3) Adding the calcification treatment powder into a sulfuric acid solution for acid leaching, performing solid-liquid separation on leached ore pulp to obtain filter residue and filtrate, adding a hydrogen peroxide solution and limestone into the filtrate for oxidation and neutralization iron precipitation, and filtering to obtain iron-containing slag and iron-removed liquid, wherein the iron-containing slag is used for recovering iron;

(4) under the condition that the temperature is 80 ℃, the iron-removed liquid obtained in the step (3) is mixed with the blast furnace gas mud and the zinc chloride according to the mass ratio of 30: 1.5-3.0, adding zinc chloride powder, stirring, reacting, precipitating for 1-2 h, and filtering to obtain calcium-magnesium slag and a zinc sulfate solution;

(5) and (4) sequentially adding the zinc sulfate solution obtained in the step (4) into an iron bicarbonate or ammonium carbonate solution for crystallization to precipitate zinc carbonate, filtering and washing, evaporating, concentrating, dehydrating, air-drying, transferring into a muffle furnace, and calcining to obtain the rubber and plastic modified additive.

As a further scheme of the invention: and (2) crushing, drying and grinding the blast furnace gas mud, the sintering machine head electro-precipitator dust and the furnace front ore groove precipitator dust in the step (1) to obtain a powdery blast furnace gas mud material with the particle size of 0.050 mm-0.07 mm.

As a further scheme of the invention: the acid leaching process in the step (4) is specifically as follows: under the condition of 70 ℃, the powder with the powdery calcification treatment is prepared by mixing the following components in a solid-to-liquid ratio of 2: adding 5g/mL of the mixed solution into 0.5-0.8 mol/L of sulfuric acid solution for leaching for 5-8 min, standing and settling for 5-8 min after leaching is finished, and then carrying out solid-liquid separation to obtain filter residue and filtrate.

As a further scheme of the invention: the step (4) of oxidizing, neutralizing and depositing iron specifically comprises the following steps: at room temperature, according to the ratio of the mass of the calcification treatment powder to the volume of the hydrogen peroxide solution being 30: 2-3 g/mL, adding 30wt% hydrogen peroxide solution into the filtrate, uniformly mixing, and then adding limestone to adjust the pH value to 5.2-5.4 to obtain iron-removed liquid and iron slag.

As a further scheme of the invention: and (3) evaporating and concentrating the zinc sulfate solution obtained in the step (5) until the supersaturation degree is 1.83g/ml, then placing the solution in ice water at the temperature of 0 ℃ for cooling and crystallizing for 10-12 h to obtain water, and dehydrating and air-drying to obtain the high-purity water-containing zinc sulfate.

The invention has the beneficial effects that:

the invention discloses a process method for preparing a rubber and plastic modified additive by using ferrous metallurgy dust and sludge, which uses saturated CO₂The water solution is leached to recover valuable zinc, impurity elements are fully leached and reacted, zinc in the gas mud exists in the form of zinc oxide, calcification treatment powder is formed to promote the leaching effect of acid leaching, and the product zinc oxide is obtained by washing, drying and firing, so that less iron and carbon in the gas mud are leached, and the product zinc oxide can be preservedThe gas mud is proved to return to sintering, and coke and iron ore concentrate are saved for iron works.

Compared with the prior art, the invention has the following advantages:

the rubber and plastic modified additive zinc oxide prepared from the ferrous metallurgy dust and mud disclosed by the invention contains abundant valuable metals, is difficult to recover and greatly reduced, has low separation cost, fully utilizes the valuable metals, improves the bad conditions that low-grade secondary zinc oxide is usually used as waste, causes a large amount of solid waste accumulation and causes serious pollution to the surrounding environment, expands the application field of the waste as the rubber and plastic modifier, fully utilizes secondary resources of blast furnace gas mud, sintering machine head electric dedusting ash and stokehole dedusting ash, is favorable for environmental protection, and has remarkable economic value and social benefit.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.