CN102992400B - Technology for preparing bismuth sulfide by utilizing bismuth-containing smoke through wet method - Google Patents
Technology for preparing bismuth sulfide by utilizing bismuth-containing smoke through wet method Download PDFInfo
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- CN102992400B CN102992400B CN201110269540.6A CN201110269540A CN102992400B CN 102992400 B CN102992400 B CN 102992400B CN 201110269540 A CN201110269540 A CN 201110269540A CN 102992400 B CN102992400 B CN 102992400B
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Abstract
The invention relates to a new technology for preparing bismuth sulfide by utilizing a bismuth-containing smoke through a wet method. The technology comprises the following steps: carrying out acidic leaching of the bismuth-containing smoke, neutralizing, hydrolyzing to remove impurities and separate the impurities comprising Pb, Cu, Zn, Si and the like, carrying out second acid dissolution, and adding sodium sulfide to transit to obtain bismuth sulfide. The technology has the advantages of simple flow, low cost, and metal utilization rate improvement, and is an economic and utile technology for producing bismuth sulfide through utilizing a bismuth-containing material.
Description
Technical field
The present invention relates to a kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, belong to the preparation field of non-ferrous metal hydrometallurgy and semiconductor nano material.
Background technology
The research and development that the preparation field of semiconductor material is new forms of energy provide important technique means.Bismuth sulfide material has storage hydrogen function, and synthesized semiconductor bismuth sulfide is all significant in science or new forms of energy application aspect.
Through retrieval, existing bismuth sulfide is prepared patent report to be had:
Zhong state invention patent application publication number CN1974406A disclosed " single stage method is prepared the method for monodispersity sodium sulphite nanoparticle " its advantage and was that the dispersion medium using is deionized water or ethanol June 6 in 2007, cheap and easy to get, environmentally safe, reaction times is short, be generally 1-4h, productive rate is generally 90%, easy and simple to handle, be easy to control, the dispersion stabilizer using is biocompatiblity molecules, it not only can improve the stability of nanoparticle to the modification on bismuth sulfide surface, also can improve the biocompatibility of nanoparticle, reduces toxicity etc.
November 26 in 2008 Zhong state invention patent application publication number CN101311385A to disclose " preparation method of bismuth sulfide whisker with the bismuth sulfide whisker preparing " be a kind of hydrothermal synthesis method that adopts.Selecting five water Bismuth trinitrates, thiocarbamide, lithium hydroxide is reaction raw materials, taking deionized water as hydro-thermal reaction medium.It is that 200-300nm, length are 20um or above bismuth sulfide whisker that the preparation method that this invention provides can obtain mean diameter.
October 7 in 2009, Zhong state invention patent application publication number CNCN101549887A disclosed a kind of synthetic method of bismuth trisulfide nanostructure " the method is taking Trichlorobismuthine, gsh as raw material; and the ethylene glycol solution that at room temperature configures Trichlorobismuthine, gsh does the initial liquid reacting; this initial liquid is placed in reactor, heats and within 8-48 hour, can obtain bar-shaped and sting spherical bismuth sulfide by the bar-shaped complexity forming as secondary structure at 120-270 DEG C.
But all there is technical process complexity in above-mentioned technique, cost is high, the technical problem at the bottom of production utilization ratio.
Summary of the invention
The object of the invention is to provide a kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, bismuth-containing flue dust process acidic leaching, and neutralizing hydrolysis removal of impurities and lead, copper, zinc, the impurity such as silicon separate, then through acid-soluble for the second time, add sodium sulphite to make the transition and obtain bismuth sulfide.This technical process is simple, and cost is low, more improves production utilization ratio, reduces production cost.
It is as follows that the present invention realizes above-mentioned purpose technical scheme:
A kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, it is characterized in that: with leaded 5%-15%, bismuth-containing 30%-60%, containing zinc 1%-5%, cupric 1%-5%, be raw material containing the bismuth-containing flue dust of silica 1 0%-20%, through acidic leaching, neutralizing hydrolysis removal of impurities separates heavy bismuth, and through acid-soluble for the second time, finally sulfuration obtains bismuth sulfide after oven dry transition; Each process is as follows:
1. acidic leaching
Bismuth-containing flue dust drying and crushing, to 150-200 order, is added in hydrochloric acid soln, then add sodium chlorate, sodium-chlor dosing; Stir, heating, leaches; Filtering separation leached mud and pickling liquor; Leached mud is plumbous silver-colored slag, send plumbous smelting procedure; Leaching condition: concentration of hydrochloric acid 1.2mol/L, sodium-chlor add-on is that slag charge weighs 9%, sodium chlorate add-on is that slag charge weighs 2.5%, liquid-solid ratio 3:1, temperature 60-65 DEG C, reaction times 3h;
2. neutralizing hydrolysis
Pickling liquor is first added to alkali lye, stir, adjust pH=1.5; Add water again, adjust pH=2.5-3, at normal temperatures, continue to stir hydrolysis reaction 0.5-1h; Filter, obtain the rear liquid of hydrolysis residue and hydrolysis; After hydrolysis, liquid returns to 1. dosing of step;
3. secondary is acid-soluble
Hydrolysis residue is joined in dilute hydrochloric acid acid-soluble, control acid-soluble terminal pH < 1, reaction times 1.6-2h, until slag charge is all dissolved, obtains clarified acid solution; Acid-soluble condition: concentration of hydrochloric acid 0.5-0.7mol/L, temperature 60-65 DEG C, liquid-solid ratio 3:1;
4. sulfuration makes the transition
In clarified acid solution, slowly control and add the saturated sodium sulfide solution configuring, adjust pH=3, normal temperature continues stirring reaction 1.5-2 hour, and press filtration obtains black precipitate bismuth sulfide, and filtrate is returned to 1. dosing of step;
5. dry sample dry
Bismuth sulfide is dried 20 hours in 60-70 DEG C of baking oven, and last comminution by gas stream obtains nano level bismuth sulfide product.
Step of the present invention 1. in, in the situation that not increasing acidity, improve chlorine ion concentration, and add a small amount of oxygenant, can make bismuth leach and plumbous silicon is stayed in slag, realize the plumbous silicon of bismuth and separate.
The present invention rationally recycles bismuth-containing flue dust, has reduced environmental pollution, and technical process is simple, and cost is low.Compared with the existing technology, the present invention has following advantage:
(1) the inventive method wide accommodation, leaded 5%-15%, bismuth-containing 30%-60%, containing zinc 1%-5%, cupric 1%-5%, all applicable containing the less material of other impurity in addition;
(2) the present invention, except comminution by gas stream part, is wet method system, and flow process is simple;
(3) equipment is simple, easy to operate, easily realizes manufacture;
(4) auxiliary material is little, saves production cost;
(5) this technique water pollution-free, noise is far below national standard, and primary acidic leaching residue, returns to the plumbous smelting system of pyrogenic process, without noxious waste pollution, is beneficial to environmental protection.
Brief description of the drawings
Accompanying drawing is in conjunction with concrete process implementing mode, detailed explanation technique trend;
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
A kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, it is characterized in that: with leaded 15%, bismuth-containing 30%, containing zinc 5%, cupric 5%, be raw material containing the bismuth-containing flue dust of silica 1 0%, through acidic leaching, neutralizing hydrolysis removal of impurities separates heavy bismuth, and through acid-soluble for the second time, finally sulfuration obtains bismuth sulfide after oven dry transition; Each process is as follows:
1. acidic leaching
By bismuth-containing flue dust drying and crushing to 150 order, add in hydrochloric acid soln, then add sodium chlorate, sodium-chlor dosing; Stir, heating, leaches; Filtering separation leached mud and pickling liquor; Leached mud is plumbous silver-colored slag, send plumbous smelting procedure; Leaching condition: concentration of hydrochloric acid 1.2mol/L, sodium-chlor add-on is that slag charge weighs 9%, sodium chlorate add-on is that slag charge weighs 2.5%, liquid-solid ratio 3:1, temperature 60 C, reaction times 3h;
The reaction wherein occurring is:
CuO+2HCl=CuCl
2+H
2O
ZnO+2HCl=ZnCl
2+H
2O
Bi
2O
3+6HCl=2BiCl
3+3H
2O
2. neutralizing hydrolysis
Pickling liquor is first added to alkali lye, stir, adjust pH=1.5; Add water again, adjust pH=2.8, at normal temperatures, continue to stir hydrolysis reaction 1h; Filter, obtain the rear liquid of hydrolysis residue and hydrolysis; After hydrolysis, liquid returns to 1. dosing of step;
The reaction wherein occurring is:
BiCl
3+2NaOH=BiOCl↓+H
2O+2NaCl
BiCl
3+H
2O=BiOCl↓+2HCl
3. secondary is acid-soluble
Hydrolysis residue is joined in dilute hydrochloric acid acid-soluble, control acid-soluble terminal pH < 1, reaction times 1.6-2h, until slag charge is all dissolved, obtains clarified acid solution; Acid-soluble condition: concentration of hydrochloric acid 0.5-0.7mol/L, temperature 60-65 DEG C, liquid-solid ratio 3:1;
The reaction wherein occurring is:
BiOCl+2HCl=BiCl
3+H
2O
4. sulfuration makes the transition
In clarified acid solution, slowly control and add the saturated sodium sulfide solution configuring, adjust pH=3, normal temperature continues stirring reaction 1.5-2 hour, and press filtration obtains black precipitate bismuth sulfide, and filtrate is returned to 1. dosing of step;
The reaction wherein occurring is:
2BiCl
3+3Na
2S=Bi
2S
3↓+6NaCl
5. dry sample dry
Bismuth sulfide is dried 20 hours in 60-70 DEG C of baking oven, and last comminution by gas stream obtains nano level bismuth sulfide product.
Embodiment 2
Bismuth flue dust composition: lead 5%, bismuth: 60%, copper: 1%, zinc: 1%, silicon-dioxide: 20%;
A kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, adopt Production Flow Chart as Fig. 1, through drying and crushing to 160 order, first hydrochloric acid being made into concentration is 1.2 mol/L solution 3L, then will be crushed to 160 object bismuth flue dust and add in solution, adds 1kg material in the ratio of liquid-solid ratio 3:1, add 25 grams of sodium chlorate, add 90 grams, sodium-chlor, 62 DEG C of temperature, reaction times 3h.Leach liquor first adds 3mol/L lye pH adjustment=1.5, add water again and adjust pH=3, continue stirring reaction filtration half an hour and obtain chlorine oxygen bismuth, this chlorine oxygen bismuth is joined in the dilute hydrochloric acid of the 0.5mol/L configuring, temperature 60 C, liquid-solid ratio 3:1, controls terminal pH=0.6, and after reaction times 1.6h, solution is dissolved to clarification.In this clear liquor, add the saturated sodium sulfide solution configuring, adjust pH=3, normal temperature continues stirring reaction 1.5 hours, filters and obtains black precipitate bismuth sulfide, and this bismuth sulfide is dried 20 hours in 65 DEG C, and rear comminution by gas stream obtains 711.0 grams of black powder bismuth sulfides.This bismuth sulfide bismuth-containing: 80.28%.The transformation efficiency that bismuth is converted into bismuth sulfide is 96.9%.
Embodiment 3
Bismuth flue dust composition: lead: 11.50%, bismuth: 51.6%, copper: 1.2%, zinc: 1.93%, silicon-dioxide: 15%;
A kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, adopt Production Flow Chart as Fig. 1, through drying and crushing to 200 order, first hydrochloric acid being made into concentration is 1.2 mol/L solution 3L, then will be crushed to 200 object bismuth flue dust and add in solution, adds 1KG material in the ratio of liquid-solid ratio 3:1, add 25 grams of sodium chlorate, add 90 grams, sodium-chlor, 65 DEG C of temperature, reaction times 3h.Leach liquor first adds 3mol/L lye pH adjustment=1.5, add water again and adjust pH=3, continue stirring reaction filtration half an hour and obtain chlorine oxygen bismuth, this chlorine oxygen bismuth is joined in the dilute hydrochloric acid of the 0.6mol/L configuring, 61 DEG C of temperature, liquid-solid ratio 3:1, controls terminal pH=0.8, and after reaction times 2.0h, solution is dissolved to clarification.In this clear liquor, add the saturated sodium sulfide solution configuring, adjust pH=3.2, normal temperature continues stirring reaction 1.5 hours, filters and obtains black precipitate bismuth sulfide, this bismuth sulfide is dried 24 hours in 65 DEG C, and rear comminution by gas stream obtains 611.6 grams of black powder bismuth sulfides.This bismuth sulfide bismuth-containing: 80.78%.The transformation efficiency that bismuth is converted into bismuth sulfide is 95.75%.
Claims (2)
1. a technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide, it is characterized in that: with leaded 5%-15%, bismuth-containing 30%-60%, containing zinc 1%-5%, cupric 1%-5%, be raw material containing the bismuth-containing flue dust of silica 1 0%-20%, through acidic leaching, neutralizing hydrolysis removal of impurities separates heavy bismuth, and through acid-soluble for the second time, finally sulfuration obtains bismuth sulfide after oven dry transition; Each process is as follows:
1. acidic leaching
Bismuth-containing flue dust drying and crushing, to 150-200 order, is added in hydrochloric acid soln, then add sodium chlorate, sodium-chlor dosing; Stir, heating, leaches; Filtering separation leached mud and pickling liquor; Leached mud is plumbous silver-colored slag, send plumbous smelting procedure; Leaching condition: concentration of hydrochloric acid 1.2mol/L, sodium-chlor add-on is that slag charge weighs 9%, sodium chlorate add-on is that slag charge weighs 2.5%, liquid-solid ratio 3:1, temperature 60-65 DEG C, reaction times 3h;
2. neutralizing hydrolysis
Pickling liquor is first added to alkali lye, stir, adjust pH=1.5; Add water again, adjust pH=2.5-3, at normal temperatures, continue to stir hydrolysis reaction 0.5-1h; Filter, obtain the rear liquid of hydrolysis residue and hydrolysis; After hydrolysis, liquid returns to 1. dosing of step;
3. secondary is acid-soluble
Hydrolysis residue is joined in dilute hydrochloric acid acid-soluble, control acid-soluble terminal pH < 1, reaction times 1.6-2h, until slag charge is all dissolved, obtains clarified acid solution; Acid-soluble condition: concentration of hydrochloric acid 0.5-0.7mol/L, temperature 60-65 DEG C, liquid-solid ratio 3:1;
4. sulfuration makes the transition
In clarified acid solution, slowly control and add the saturated sodium sulfide solution configuring, adjust pH=3, normal temperature continues stirring reaction 1.5-2 hour, and press filtration obtains black precipitate bismuth sulfide, and filtrate is returned to 1. dosing of step;
5. dry sample dry
Bismuth sulfide is dried 20 hours in 60-70 DEG C of baking oven, and last comminution by gas stream obtains nano level bismuth sulfide product.
2. a kind of technique of utilizing bismuth-containing flue dust wet method to prepare bismuth sulfide according to claim 1, is characterized in that: step 1. in, in the situation that not increasing acidity, improve chlorine ion concentration, and add a small amount of oxygenant, bismuth is leached and plumbous silicon is stayed in slag, realize the plumbous silicon of bismuth and separate.
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| CN101492179B (en) * | 2009-03-10 | 2011-06-08 | 武汉理工大学 | Bismuth sulfide material synthesis method |
Non-Patent Citations (2)
| Title |
|---|
| 从铜吹炉烟灰中回收金属铋的工艺;俞宗衡;《化学世界》;19871231(第10期);465-468 * |
| 俞宗衡.从铜吹炉烟灰中回收金属铋的工艺.《化学世界》.1987,(第10期),465-468. |
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