阅读说明：本技术 一种钢铁冶金尘泥制备橡塑复合改性添加剂的工艺方法 (Process method for preparing rubber-plastic composite modified additive from ferrous metallurgy dust and mud ) 是由 丁宝文 于 2019-11-14 设计创作，主要内容包括：本发明属于属于氧化锌技术领域,尤其是一种活性氧化锌的制备方法,本发明公开的一种活性氧化锌的制备方法,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,采用包覆微胶囊的方法制备活性氧化锌,具有普通氧化锌所无法比较的特殊性和用途,可用于紫外光遮蔽材料、抗菌剂、荧光材料、光催化材料等的制备。(The invention belongs to the technical field of zinc oxide, and particularly relates to a preparation method of active zinc oxide.)

1. A preparation method of active zinc oxide is characterized by comprising the following steps:

(1) mixing 100-110 parts of blast furnace gas mud and 0.5-0.9 part of sodium dodecyl benzene sulfonate into dilute emulsion by using 300 parts of water, putting the dilute emulsion and 77-86 parts of hydrochloric acid solution with the mass fraction of 12-13 into a corrosion-resistant reaction kettle, stirring and reacting for 0.5h to obtain mixed aqueous solution containing zinc chloride, filtering to obtain filter cake impurities and clear zinc chloride solution, adding 12-14 parts of zinc hydroxide and 8-11 parts of calcium chloride into the obtained zinc chloride solution, stirring uniformly and dispersing, filtering out precipitates to obtain clear filtrate, feeding the obtained clear filtrate into an evaporator, heating to 100 ℃ to evaporate to obtain a liquid solution which is a saturated zinc chloride solution, discharging the saturated zinc chloride solution, feeding the saturated zinc chloride solution into a condenser to crystallize, and separating out zinc chloride crystals; air-drying and crushing the obtained zinc chloride crystal to obtain pretreated zinc subchloride;

weighing and subpackaging the pretreated zinc hypochlorite, sodium carbonate, salt and shellac obtained in the step (1), then respectively pretreating, drying at 150-180 ℃ for 10-14 h to mix uniformly, putting the three raw materials into a planetary mill for ball milling treatment, then carrying out heat treatment at 500-600 ℃ for 1-2 h, then dispersing in an ultrasonic cleaner, then repeatedly carrying out suction filtration on the semi-finished product in a water circulation vacuum pump, removing soluble impurities in a suction filtration bottle along with distilled water, and finally putting the suction-filtered sample into an oven for drying to obtain white milk powder;

weighing and mixing the white milk powder obtained in the step (2), glycerol, epoxidized soybean oil and an antioxidant, heating until mutual dissolution to form an oil phase liquid, dropwise adding alkali liquor accounting for 5.5-6.7% of the total weight of the oil phase liquid into the oil phase under the condition of high-speed shearing, stirring at a low speed for saponification continuously after dropwise adding, wherein the high-speed shearing speed is 3000-10000 rpm, adding calcium ricinoleate accounting for 24.5-26.1% of the total weight of the alkali liquor, stirring to form a suspension emulsion, adding the alkali liquor into the suspension emulsion, heating to 55-60 ℃, stirring for 0.5-1 h to obtain an active dispersion, adding acid to adjust the pH value to 7-8, then carrying out fluidized bed spray granulation while hot to form microcapsule particles coated by starch particles, and drying at 50-60 ℃ for 1-2 h to obtain the active zinc oxide.

2. The preparation method of the active zinc oxide according to claim 1, wherein the ball milling treatment in the step (2) is performed at a ball-material mass ratio of 10:1, a ball mill rotation speed of 1000-1200 rpm, and a ball milling time of 2-4 h.

3. The method of claim 1, wherein the antioxidant is one of diisooctyl phosphite, vitamin E, antioxidant MBZ, and trioctyl borate.

4. The preparation method of active zinc oxide according to claim 1, wherein the weight ratio of the pre-treated zinc hypochlorite, the sodium carbonate, the salt and the shellac weighed and dispensed in the step (2) is 10: 10-15: 30-50: 3.

5. The preparation method of active zinc oxide according to claim 1, wherein the weight ratio of the weighed and subpackaged white milk powder, glycerin, epoxidized soybean oil and antioxidant in the step (3) is 10: 10-15: 30-50: 0.3.

6. The method for preparing activated zinc oxide according to claim 1, wherein the alkali solution in step (3) is an aqueous solution of sodium hydroxide or potassium hydroxide with a mass concentration of 10-20%.

Technical Field

The invention belongs to the technical field of zinc oxide, and particularly relates to a process method for preparing a rubber-plastic composite modified additive by using ferrous metallurgy dust and sludge.

Background

Zinc oxide is an oxide of zinc. Is insoluble in water and soluble in acid and strong base. Zinc oxide is a commonly used chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint, coating, ointment, adhesive, food, batteries, flame retardant and the like. The zinc oxide has large energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the semiconductor field. In addition, the zinc oxide of fine particles also starts to function in the related art as a nano material.

The active zinc oxide is a novel multifunctional inorganic material, shows a plurality of special functions in the aspects of catalysis, optics, magnetism, mechanics and the like in recent years, has important application value in a plurality of fields of ceramics, chemical engineering, electronics, optics, biology, medicine and the like, and has specificity and application which can not be compared with common zinc oxide.

The zinc oxide is used as an auxiliary agent necessary for a vulcanization system, the filling amount of the zinc oxide is higher, generally about 5 parts, and the zinc oxide has large specific gravity and large filling amount, so that the zinc oxide has great influence on the density of a rubber material. The larger the weight of dynamically used products such as tires and the like is, the larger the heat generation and rolling resistance of the products are, which is unfavorable for the service life and energy consumption of the products, and especially for the modern society, people put high requirements on the safety and environmental protection of the products. Those skilled in the art are keenly to develop a method for preparing active zinc oxide to reduce the production cost so as to meet the requirements of larger market and higher performance.

Disclosure of Invention

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

The invention is realized by the following technical scheme:

a preparation method of active zinc oxide comprises the following steps:

(1) mixing 100-110 parts of blast furnace gas mud and 0.5-0.9 part of sodium dodecyl benzene sulfonate into dilute emulsion by using 300 parts of water, putting the dilute emulsion and 77-86 parts of hydrochloric acid solution with the mass fraction of 12-13 into a corrosion-resistant reaction kettle, stirring and reacting for 0.5h to obtain mixed aqueous solution containing zinc chloride, filtering to obtain filter cake impurities and clear zinc chloride solution, adding 12-14 parts of zinc hydroxide and 8-11 parts of calcium chloride into the obtained zinc chloride solution, stirring uniformly and dispersing, filtering out precipitates to obtain clear filtrate, feeding the obtained clear filtrate into an evaporator, heating to 100 ℃ to evaporate to obtain a liquid solution which is a saturated zinc chloride solution, discharging the saturated zinc chloride solution, feeding the saturated zinc chloride solution into a condenser to crystallize, and separating out zinc chloride crystals; air-drying and crushing the obtained zinc chloride crystal to obtain pretreated zinc subchloride;

(2) weighing and subpackaging the pretreated zinc hypochlorite, sodium carbonate, salt and shellac obtained in the step (1), then respectively pretreating, drying at 150-180 ℃ for 10-14 h to mix uniformly, putting the three raw materials into a planetary mill for ball milling treatment, then carrying out heat treatment at 500-600 ℃ for 1-2 h, then dispersing in an ultrasonic cleaner, then repeatedly carrying out suction filtration on the semi-finished product in a water circulation vacuum pump, removing soluble impurities in a suction filtration bottle along with distilled water, and finally putting the suction-filtered sample into an oven for drying to obtain white milk powder;

(3) weighing and mixing the white milk powder obtained in the step (2), glycerol, epoxidized soybean oil and an antioxidant, heating until mutual dissolution to form an oil phase liquid, dropwise adding alkali liquor accounting for 5.5-6.7% of the total weight of the oil phase liquid into the oil phase under the condition of high-speed shearing, stirring at a low speed for saponification continuously after dropwise adding, wherein the high-speed shearing speed is 3000-10000 rpm, adding calcium ricinoleate accounting for 24.5-26.1% of the total weight of the alkali liquor, stirring to form a suspension emulsion, adding the alkali liquor into the suspension emulsion, heating to 55-60 ℃, stirring for 0.5-1 h to obtain an active dispersion, adding acid to adjust the pH value to 7-8, then carrying out fluidized bed spray granulation while hot to form microcapsule particles coated by starch particles, and drying at 50-60 ℃ for 1-2 h to obtain the active zinc oxide.

As a further scheme of the invention: the ball milling treatment in the step (2) is carried out at a ball material mass ratio of 10:1, a ball mill rotation speed of 1000-1200 rpm and ball milling time of 2-4 h.

As a further scheme of the invention: the antioxidant is one of diisooctyl phosphite, vitamin E, an anti-aging agent MBZ or trioctyl borate.

As a further scheme of the invention: and (3) weighing and subpackaging the pretreated zinc hypochlorite, the sodium carbonate, the salt and the shellac in the step (2) according to the mass ratio of 10: 10-15: 30-50: 3.

As a further scheme of the invention: the weight ratio of the weighed and subpackaged white milk powder, the glycerol, the epoxidized soybean oil and the antioxidant in the step (3) is 10: 10-15: 30-50: 0.3.

As a further scheme of the invention: the alkali liquor in the step (3) is an aqueous solution of sodium hydroxide or potassium hydroxide with the mass concentration of 10-20%.

The invention has the beneficial effects that:

the preparation method of the active zinc oxide disclosed by the invention improves the recovery rate of zinc in the blast furnace gas mud, coats the zinc oxide and increases the particle surface of the zinc oxide so as to improve the action effect of the zinc oxide. Meanwhile, the zinc oxide has the characteristics of good rolling property and excellent dispersibility by virtue of larger specific surface and lower dosage, has small particle size, light and loose structure, large nitrogen adsorption specific surface area, uniform distribution, large contact area and larger interface reaction opportunity, is used as an ultraviolet stabilizer in the rubber and plastic industry, and can better improve the atmospheric resistance of the polymer. Has the advantages of simple equipment, convenient operation, easily controlled process, high product quality, fine and uniform crystal grains and the like. Zinc hydroxide and calcium chloride are added into the obtained zinc chloride solution, so that chloride, zinc sulfate and zinc sulfide in the solution are converted into hydroxide, calcium sulfate and calcium sulfide for precipitation, the stability and the dispersibility of active oxidizability are improved by introducing epoxy soybean oil and the like, and the active zinc oxide has a higher specific surface area by microcapsule modification. The zinc oxide prepared by the mechanical method has higher purity, and can meet the use requirement of high-performance zinc oxide in the fields of feed and coating.

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

the active zinc oxide obtained by direct seeding by the preparation method disclosed by the invention has large specific surface area, high activity and lower price than common zinc oxide, the active zinc oxide is prepared by synthesizing zinc oxide, glycerin, epoxy soybean oil and the like by a mechanical method, and then the active zinc oxide is prepared by pyrolysis because of the characteristics of the blast furnace gas mud body, such as zinc content and high carbon content, and most of zinc is separated from the blast furnace gas mud, so that the environment is saved and protected, the energy waste is less, the activation method is simple and easy to implement, and the environment is protected.

Detailed Description

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