CN102234116A

CN102234116A - Method for preparing nano white carbon black by utilizing iron tailings

Info

Publication number: CN102234116A
Application number: CN2011100713734A
Authority: CN
Inventors: 沈毅; 李锋锋; 张明熹; 李红生; 唐晓飞; 王庆辉
Original assignee: Hebei United University
Current assignee: Hebei United University
Priority date: 2011-03-16
Filing date: 2011-03-16
Publication date: 2011-11-09
Anticipated expiration: 2031-03-16
Also published as: CN102234116B

Abstract

The invention relates to a method for preparing nano white carbon black by taking iron tailings as raw materials. The method comprises the following steps of: mixing and calcining the iron tailings activated at a high temperature and caustic soda at the temperature of 400-500 DEG C, then directly pouring the mixture into a water bath at the temperature of 70-90 DEG C to fully react, filtering to obtain a sodium silicate solution, adding a dispersing agent NaCl and a surfactant normal butanol into the sodium silicate solution, slowly dropwise adding 5-10wt% HCl for acidification under the stirring condition to generate massive white flocculent precipitates, and then ageing, filtering, washing and drying, thus the nano white carbon black product is obtained. The method is simple to operate and has low cost, high product yield and fine particle size and is applicable to industrialization production.

Description

A kind of method of utilizing iron tailings to prepare Nano carbon white

Technical field

The present invention relates to the method that a kind of iron tailings prepares Nano carbon white, belong to field of inorganic nonmetallic material.

Background technology

Along with continuous progress in science and technology, industrial production constantly develops towards intelligent, less energy-consumption, high environmental protection direction, how to realize making full use of of existing resource, has become the problem of various circles of society's extensive concern.Iron tailings is a kind of solid waste, and along with the fast development of Iron And Steel Industry, iron tailings shared ratio in industrial solid castoff is also increasing.Under the restriction of factors such as technology and ore-dressing technique, the iron ore deposit rate of recovery is on the low side in history in China.Characteristics such as the quantity of adding iron tailings itself is huge, structure properties is complicated, type is more make it very low in China's utilization ratio, only are 7%.Causing puzzlement on the one hand our environment, also is the waste of resource on the other hand.It not only makes the Mineral resources of China not be fully used, and has also taken a large amount of land resources, has consumed a large amount of funds, has influenced economic benefit of enterprises.Main component is SiO in the iron tailings ₂And a spot of Fe ₂O ₃, MgO, Al ₂O ₃, CaO etc. (place of production difference, composition are slightly variant).Wherein, SiO ₂Content generally greater than 50wt%, have very big value of exploiting and utilizing.Therefore, from iron tailings, extract white carbon black (being hydrated SiO 2), can realize resource effectively utilization to a greater extent, and improve value-added content of product.

Application number is that 200710012954.4 patent of invention has proposed a kind of method of utilizing iron tailings to prepare white carbon black, steps such as this method is molten through alkali, acidifying, precipitation, washing are prepared white carbon black, but this method is because the alkali solubility temperature is lower, be 50-120 ℃, the productive rate of white carbon black is not high, and product granularity is also thicker.Application number is that 96115532.9 patent of invention has proposed a kind of method of producing active carbon white with coal gangue, this method adopts comminuted coal spoil and soda ash batch mixing, and, shrend molten, soak steps such as molten, concentrated, acidifying, ageing, washing and prepare white carbon black in 1400-1500 ℃ of high temperature smelting, because this method needs the high temperature smelting molten, therefore energy consumption is too high, side reaction also taking place under the hot conditions in addition easily, cause impurity generations such as indissoluble silicate, reduces the purity and the productive rate of white carbon black product.

The present invention is different with above-mentioned report, is primarily aimed at the present situation of utilizing of China's iron tailings, has proposed a kind of new technology and novel process of utilizing iron tailings to prepare Nano carbon white.This technology has characteristics such as technology is simple, energy consumption is low, cost is low, product cut size can reach nano level, added value of product height, comprehensive utilization of tailing rate height; be suitable for suitability for industrialized production, all have crucial meaning for the development of comprehensive utilization, environment protection and even the stake holder economy of iron tailings.

Summary of the invention

It is the method for feedstock production Nano carbon white with the iron tailings that the present invention relates generally to a kind of, and concrete summary of the invention is as follows:

1) calcining and activating of iron tailings: below iron tailings ball milling to 200 order, 800～900 ℃ of calcinings of retort furnace, 2～4h.

2) iron tailings and caustic soda mixed calcining: iron tailings after will activating and solid NaOH are by massfraction iron tailings: NaOH=100: 200～300 mix, and place retort furnace in 400～500 ℃ of calcining 0.5～2h.

3) prepare silicon acid sodium solution: above-mentioned compound is taken out under calcining temperature by quality than compound: water=15: 100～200 are poured quenching 70～90 ℃ the water rapidly into, and react 0.5～2h under whipped state, make SiO ₂Fully react with NaOH, after the filtration, gained filtrate is sodium silicate solution.

4) precipitating Nano carbon white: in above-mentioned sodium silicate solution, press mass ratio activation iron tailings: NaCl=100: 40～60, add solid NaCl as dispersion agent, sodium silicate solution by volume: propyl carbinol=100: 4～6, add propyl carbinol as tensio-active agent, and the HCl acidifying of Dropwise 5～10wt% under slow whipped state, be adjusted to 7～9 until the pH value of solution value, produce a large amount of white flockss, ageing 1～2h filters the thick product that obtains Nano carbon white.

5) washing of white carbon black: the thick product of white carbon black is washed Na in checking product ⁺, Cl ^-Till content is qualified, Na wherein ⁺＜1wt%, Cl ^-＜1wt%.

6) calcining of white carbon black: the product after the washing is pulverized in 100～200 ℃ of drying 1～2h, obtains the finished product.

Description of drawings

Fig. 1 prepares the process flow sheet of Nano carbon white for iron tailings of the present invention.

Fig. 2 is the sem photograph with the Nano carbon white of preparing under example 1 processing condition.

Embodiment

The present invention is described in detail below in conjunction with embodiment, and the present invention is not limit by these manufacturing examples.

Example 1

Below iron tailings ball milling to 200 order, 850 ℃ of calcinings of retort furnace 3h mixes the 100g iron tailings after the activation with the NaOH of 300g, and places retort furnace in 500 ℃ of calcining 1h; Pour 4500ml rapidly into after compound after the calcining taken out under the calcining temperature, in 90 ℃ of water-baths, and stirring reaction 2h, filter, obtain sodium silicate solution; In sodium silicate solution, add 60gNaCl and propyl carbinol 200ml, and the HCl acidifying of Dropwise 5 wt% under slow whipped state, be adjusted to 7 until the pH value of solution value, produce a large amount of white flockss, ageing 1h filters the thick product that obtains Nano carbon white; The thick product of white carbon black is washed, checked Cl ^-, Na ⁺Content is all less than till the 1wt%; Pulverize in 200 ℃ of dry 2h product washing back, obtains the finished product, and product cut size can reach 30～50nm.

Example 2

Below iron tailings ball milling to 200 order, 800 ℃ of calcinings of retort furnace 4h mixes the 100g iron tailings after the activation with the NaOH of 250g, and places retort furnace in 400 ℃ of calcining 2h; Pour 3000ml rapidly into after compound after the calcining taken out under the calcining temperature, in 80 ℃ of water-baths, and stirring reaction 1h, filter, obtain sodium silicate solution; Add 50gNaCl and propyl carbinol 150ml in sodium silicate solution, and drip the HCl acidifying of 10wt% under slow whipped state, be adjusted to 9 until the pH value of solution value, produce a large amount of white flockss, ageing 1.5h filters the thick product that obtains Nano carbon white; The thick product of white carbon black is washed, checked Cl ^-, Na ⁺Content is all less than till the 1wt%; Pulverize in 200 ℃ of dry 1h product washing back, obtains the finished product, and product cut size can reach 50～100nm.

Example 3

Below iron tailings ball milling to 200 order, 900 ℃ of calcinings of retort furnace 3h mixes the 100g iron tailings after the activation with the NaOH of 200g, and places retort furnace in 450 ℃ of calcining 1h; Pour 2000ml rapidly into after compound after the calcining taken out under the calcining temperature, in 70 ℃ of water-baths, and stirring reaction 0.5h, filter, obtain sodium silicate solution; Add 45gNaCl and propyl carbinol 90ml in sodium silicate solution, and drip the HCl acidifying of 10wt% under slow whipped state, be adjusted to 8 until the pH value of solution value, produce a large amount of white flockss, ageing 1h filters the thick product that obtains Nano carbon white; The thick product of white carbon black is washed, checked Cl ^-, Na ⁺Content is all less than till the 1wt%; Pulverize in 100 ℃ of dry 2h product washing back, obtains the finished product, and product cut size can reach 50～80nm.

Claims

1. method for preparing Nano carbon white from iron tailings is characterized in that its processing step is:

Below iron tailings ball milling to 200 order, and in 800～900 ℃ of calcinings of retort furnace, 2～4h activation, iron tailings after the activation and solid NaOH activate iron tailings: NaOH=100 by mass ratio: 200～300 mix, place retort furnace in 400～500 ℃ of calcining 0.5～2h, above-mentioned compound directly takes out under calcining temperature, and by quality than compound: water=15: 100～200 are poured into rapidly in 70～90 ℃ the water and are cooled off, and under whipped state, react 0.5～2h, after the filtration, gained filtrate is sodium silicate solution, in sodium silicate solution, press mass ratio activation iron tailings: NaCl=100: 40～60, add solid NaCl and make dispersion agent, sodium silicate solution by volume: propyl carbinol=100: 4～6, add propyl carbinol and make to show promoting agent, and the HCl acidifying of Dropwise 5～10wt% under slow whipped state, be adjusted to 7～9 until the pH value of solution value, produce a large amount of white flockss, ageing 1～2h, filtration obtains the thick product of Nano carbon white, the thick product of white carbon black is washed Na in checking product ⁺, Cl ^-Till content is qualified, Na wherein ⁺＜1wt%, Cl ^-＜1wt%, the product after the washing pulverize in 100～200 ℃ of drying 1～2h, obtain the finished product.