CN104370524A - Environment-friendly rare-earth sintered brick prepared from micro/nano CeO2 and ZrO2 powder by doping lead zinc tailings - Google Patents
Environment-friendly rare-earth sintered brick prepared from micro/nano CeO2 and ZrO2 powder by doping lead zinc tailings Download PDFInfo
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- CN104370524A CN104370524A CN201410580188.1A CN201410580188A CN104370524A CN 104370524 A CN104370524 A CN 104370524A CN 201410580188 A CN201410580188 A CN 201410580188A CN 104370524 A CN104370524 A CN 104370524A
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Abstract
The invention provides a method for preparing an environment-friendly rare-earth sintered brick from micro/nano CeO2 and ZrO2 powder by doping lead zinc tailings, which comprises the following steps: by using the lead zinc tailings, clay and a curing agent as raw materials, adding water, uniformly mixing, carrying out extrusion forming, drying, and sintering for setting, thereby obtaining the environment-friendly rare-earth sintered brick. The method can lower the sintering temperature to perform the energy-saving function, can effectively cure the heavy metal ions in the lead zinc tailings, and ensures no damage to the environment on the premise of implementing waste utilization. The method is simple and low in cost, has favorable economic benefit and environmental benefit, and can be well put into large-scale production.
Description
Technical field
The invention belongs to environment and Material Field, be specifically related to one and utilize micro-nano CeO
2and ZrO
2powder doping Pb-Zn tailings prepares the method for environment-friendly type rare earth vitrified brick.
Background technology
At present, the annual mine tailing generation of China is about 100,000,000 tons, a large amount of mine tailing the other side not only will take soil in large quantities, deposit at substantial and overhead charges, hazardous and noxious substances simultaneously in mine tailing, particularly heavy metal is after weathering and rain, Transport And Transformation can occur, and the ecotope of periphery is produced to the destruction of unrepairable.Therefore scientifically recycle resource of tailings, turn waste into wealth, accomplish that two harvests of environmental benefit and economic benefit are a kind of selection of the best.
At present, Pb-Zn tailings has been applied in the production of some material of construction, but the heavy metal substance in mine tailing is not processed especially in these recoverying and utilizing methods, just it can be used as a kind of raw material simply to use, heavy metal substance Transport And Transformation can not be solved so well and then environment is produced to the problem polluted.
Due to CeO
2and ZrO
2at high temperature can react with some heavy metals, generate metal ion-CeO
2with metal ion-ZrO
2etc. stable soluble solids, can effectively reduce Heavy metals problem.Simultaneously due to nano Ce O
2middle Ce
3+and Ce
4+between reversible transition process along with the generation of oxygen vacancies and elimination, thus there is fabulous storage oxygen and the ability of oxygen release, simple CeO
2structural stability poor, and the demand of catalyzed oxidation at a lower temperature cannot be met, but as the CeO doped with metal ion and nonmetallic ion
2and ZrO
2when forming sosoloid, due to lattice deformity and surface imperfection, CeO can be caused
2and ZrO
2catalytic performance at a lower temperature, and then catalyticing decomposition action can be produced to some organic pollutants such as the CO in air, oxynitride and benzene class materials, positive effect is produced to purifying air and sewage disposal.We use CeO in the present invention
2and ZrO
2as solidifying agent, after high temperature sintering, effectively can solidify the heavy metal substance in Pb-Zn tailings, while the sintering temperature reducing rare earth vitrified brick, also create the effect of purifying air further, by this heavy metals immobilization technology, we successfully prepare a kind of environment-friendly type rare earth vitrified brick.
Through retrieval, at home and abroad there is no utilization is raw material with Pb-Zn tailings, with CeO
2and ZrO
2for solidifying agent, prepare a kind of method of environment-friendly type rare earth vitrified brick, this project belongs to the technology of first research invention both at home and abroad.Main raw material(s) (Pb-Zn tailings and clay) involved in the present invention is at China's rich reserves, simple and the easy handling of the preparation method used, Pb-Zn tailings waste can be recycled, the problem of effective solution heavy metal contamination, economic benefit is aobvious and environmental benefit is outstanding, has good application value.
Summary of the invention
One is the object of the present invention is to provide to utilize micro-nano CeO
2and ZrO
2powder doping Pb-Zn tailings prepares the method for environment-friendly type rare earth vitrified brick, obtained environment-friendly type rare earth vitrified brick can reduce sintering temperature, serve energy-conservation effect, effectively can solidify the heavy metal ion in Pb-Zn tailings simultaneously, while realizing utilization of waste material, ensure that not destroying environment.Its preparation method is simple, with low cost, has good economic benefit and environmental benefit, can be produced by scale of input well.
For achieving the above object, the present invention adopts following technical scheme:
One utilizes micro-nano CeO
2and ZrO
2environment-friendly type rare earth vitrified brick prepared by powder doping Pb-Zn tailings comprises following raw material: Pb-Zn tailings 70 ~ 80wt%, clay 19 ~ 29wt%, solidifying agent 1wt%; Described solidifying agent is CeO
2and ZrO
2.
CeO in described solidifying agent
260 ~ 70 wt%, ZrO
230 ~ 40 wt%.
One utilizes micro-nano CeO
2and ZrO
2powder doping Pb-Zn tailings prepares the method for environment-friendly type rare earth vitrified brick as above: after Pb-Zn tailings, clay, solidifying agent and water being mixed, through extrusion forming, drying and sintering sizing, and obtained described environment-friendly type rare earth vitrified brick.
Concrete steps are as follows:
(1) Pb-Zn tailings, clay and solidifying agent are crossed 0.075mm square hole sieve;
(2) in the water of Pb-Zn tailings, clay and solidifying agent total mass 15%, add solidifying agent, stir after 30 minutes, then add Pb-Zn tailings and clay, stir, 20MPa extrusion forming, 100 DEG C of dry 6-8 hour, 950 DEG C sinter 2 hours, obtain described environment-friendly type rare earth vitrified brick.
The rare earth vitrified brick of the environment-friendly type that this method is prepared, can re-use environmentally harmful waste, and prepared environment-friendly type rare earth vitrified brick meets the standard of GB5101-2003 " fired common brick " Plays strength grade MU30.According to solid waste Leaching measuring method (HJ/T 299-2007), Leaching experiment is carried out to mine tailing, carry out leaching ability of heavy metal situation by ICP method to goods to detect, result shows, heavy metal ion leaching concentration meets GB5085-1996 " Hazardous wastes judging standard-leaching characteristic identification ", even reach I class water requirement in GB3838-2002 " water environment quality standard ", heavy metal ion leaching concentration is much smaller than the leaching concentration of Pb-Zn tailings rare earth vitrified brick not adding solidifying agent.Illustrate and thisly utilize micro-nano CeO
2and ZrO
2the method that powder doping Pb-Zn tailings prepares environment-friendly type rare earth vitrified brick overcomes the deficiency in traditional Application way, while the sintering temperature reducing rare earth vitrified brick, the heavy metal ion in waste can also be solidified, reduce and even stopped because acid rain corrosion and body of wall damage the Heavy metals that causes to the destruction of environment.In addition, the solidifying agent in body of wall can also part is harmful in catalytic decomposition air organic pollutant, if can be applied to air and sewage treatment area in large quantities, will produce active influence to environment.And its preparation method is simple, with low cost, there is good economic benefit, can be produced by scale of input well.
Remarkable advantage of the present invention is:
(1) raw material and technological innovation: be raw material with Pb-Zn tailings, with CeO
2and ZrO
2as solidifying agent, while reduction sintering temperature, the problem that heavy metal substance runs off effectively can be controlled, the CeO simultaneously produced
2and ZrO
2sosoloid produces positive effect to purifying air, can also be applied in sewage disposal, and its method is simple, has very strong operability, can be produced by popularization.
(2) through retrieval, at home and abroad there is no and utilize micro-nano CeO
2and ZrO
2powder doping Pb-Zn tailings prepares the report of environment-friendly type rare earth vitrified brick, and this project belongs to the technology of first research invention both at home and abroad.
(3) lower production cost: main raw material(s) is Pb-Zn tailings, and it results from the process of mining in a large number, be easy to obtain, cost is very low, and economic benefit is very remarkable, has market competition ability fixed very by force.
Embodiment
The weight proportion of composition of raw materials is: Pb-Zn tailings 70 ~ 80wt%, clay 19 ~ 29wt%, solidifying agent 1wt%.
Utilization utilizes micro-nano CeO
2and ZrO
2preparation method's concrete steps that powder doping Pb-Zn tailings prepares environment-friendly type rare earth vitrified brick are:
(1) after three kinds of raw materials are crossed 0.075mm square hole sieve, solidifying agent is joined in the water of raw material total mass 15%, stir after 30 minutes, obtain the suspension of solidifying agent;
(2) in suspension, add Pb-Zn tailings and clay and stir, obtained idiosome;
(3) idiosome is carried out extrusion forming under the pressure of 20MPa, obtained shaping idiosome;
(4) the dry 6-8 hour of environment of 100 DEG C is placed at shaping idiosome;
(5) environment dried shaping idiosome being placed in 950 DEG C is incubated 2 hours, namely obtains environment-friendly type rare earth vitrified brick after sinter molding.
embodiment 1
The weight proportion of composition of raw materials: Pb-Zn tailings 70wt%, clay 29wt%, solidifying agent 1wt%(cerium dioxide 60wt%, zirconium dioxide 40wt%), by formula, three kinds of raw materials are weighed, after three kinds of raw materials are crossed 0.075mm square hole sieve, solidifying agent is joined in the water of starting material total mass 15%, stir after 30 minutes, add Pb-Zn tailings again and clay stirs, and under the pressure of 20MPa, carry out extrusion forming, in the environment of 100 DEG C after dry 6-8 hour, be placed in the environment of 950 DEG C and be incubated 2 hours, after sinter molding, namely obtain environment-friendly type rare earth vitrified brick.
Prepare every character of rare earth vitrified brick as shown in table 1-1, it meets the standard of GB5101-2003 " fired common brick " Plays strength grade MU30.According to solid waste Leaching measuring method (HJ/T 299-2007), Leaching experiment is carried out to goods, detect by ICP method heavy metal stripping situation, result is as shown in table 1-2, heavy metal ion leaching concentration meets GB5085.3-2007 " Hazardous wastes judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion reaches I class water requirement in GB3838-2002 " water environment quality standard ", and heavy metal ion leaching concentration is much smaller than the leaching concentration of Pb-Zn tailings rare earth vitrified brick not adding solidifying agent.
The character of table 1-1 vitrified brick experiment
Table 1-2 clinker leaching liquor analytical results (mg/L)
Embodiment 2
The weight proportion of composition of raw materials: Pb-Zn tailings 80wt%, clay 19wt%, solidifying agent 1wt%(cerium dioxide 60wt%, zirconium dioxide 40wt%), by formula, three kinds of raw materials are weighed, after three kinds of raw materials are crossed 0.075mm square hole sieve, solidifying agent is joined in the water of starting material total mass 15%, stir after 30 minutes, add Pb-Zn tailings again and clay stirs, and under the pressure of 20MPa, carry out extrusion forming, in the environment of 100 DEG C after dry 6-8 hour, be placed in the environment of 950 DEG C and be incubated 2 hours, after sinter molding, namely obtain environment-friendly type rare earth vitrified brick.
Prepare every character of rare earth vitrified brick as shown in table 2-1, it meets the standard of GB5101-2003 " fired common brick " Plays strength grade MU30.According to solid waste Leaching measuring method (HJ/T 299-2007), Leaching experiment is carried out to goods, detect by ICP method heavy metal stripping situation, result is as shown in table 2-2, heavy metal ion leaching concentration meets GB5085.3-2007 " Hazardous wastes judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion reaches I class water requirement in GB3838-2002 " water environment quality standard ", and heavy metal ion leaching concentration is much smaller than the leaching concentration of Pb-Zn tailings rare earth vitrified brick not adding solidifying agent.
The character of table 2-1 vitrified brick experiment
Table 2-2 clinker leaching liquor analytical results (mg/L)
Embodiment 3
The weight proportion of composition of raw materials: Pb-Zn tailings 75wt%, clay 24wt%, solidifying agent 1wt%(cerium dioxide 70wt%, zirconium dioxide 30wt%), by formula, three kinds of raw materials are weighed, after three kinds of raw materials are crossed 0.075mm square hole sieve, solidifying agent is joined in the water of starting material total mass 15%, stir after 30 minutes, add Pb-Zn tailings again and clay stirs, and under the pressure of 20MPa, carry out extrusion forming, in the environment of 100 DEG C after dry 6-8 hour, be placed in the environment of 950 DEG C and be incubated 2 hours, after sinter molding, namely obtain environment-friendly type rare earth vitrified brick.
Prepare every character of rare earth vitrified brick as shown in table 3-1, it meets the standard of GB5101-2003 " fired common brick " Plays strength grade MU30.According to solid waste Leaching measuring method (HJ/T 299-2007), Leaching experiment is carried out to goods, detect by ICP method heavy metal stripping situation, result is as shown in table 3-2, heavy metal ion leaching concentration meets GB5085.3-2007 " Hazardous wastes judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion reaches I class water requirement in GB3838-2002 " water environment quality standard ", and heavy metal ion leaching concentration is much smaller than the leaching concentration of Pb-Zn tailings rare earth vitrified brick not adding solidifying agent.
The character of table 3-1 vitrified brick experiment
Table 3-2 clinker leaching liquor analytical results (mg/L)
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. one kind utilizes micro-nano CeO
2and ZrO
2environment-friendly type rare earth vitrified brick prepared by powder doping Pb-Zn tailings, is characterized in that: comprise following raw material: Pb-Zn tailings 70 ~ 80wt%, clay 19 ~ 29wt%, solidifying agent 1wt%; Described solidifying agent is CeO
2and ZrO
2.
2. according to claim 1ly utilize micro-nano CeO
2and ZrO
2environment-friendly type rare earth vitrified brick prepared by powder doping Pb-Zn tailings, is characterized in that: CeO in described solidifying agent
260 ~ 70 wt%, ZrO
230 ~ 40 wt%.
3. one kind utilizes micro-nano CeO
2and ZrO
2powder doping Pb-Zn tailings prepares the method for environment-friendly type rare earth vitrified brick as claimed in claim 1, it is characterized in that: after Pb-Zn tailings, clay, solidifying agent and water are mixed, through extrusion forming, drying and sintering sizing, obtained described environment-friendly type rare earth vitrified brick.
4. method according to claim 3, is characterized in that: concrete steps are as follows:
(1) Pb-Zn tailings, clay and solidifying agent are crossed 0.075mm square hole sieve;
(2) in the water of Pb-Zn tailings, clay and solidifying agent total mass 15%, add solidifying agent, stir after 30 minutes, then add Pb-Zn tailings and clay, stir, 20MPa extrusion forming, 100 DEG C of dry 6-8 hour, 950 DEG C sinter 2 hours, obtain described environment-friendly type rare earth vitrified brick.
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|---|---|---|---|
| CN201410580188.1A CN104370524B (en) | 2014-10-27 | 2014-10-27 | Utilize micro-nano CeO 2and ZrO 2powder doping Pb-Zn tailings prepares environment-friendly type rare earth vitrified brick |
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|---|---|---|---|
| CN201410580188.1A CN104370524B (en) | 2014-10-27 | 2014-10-27 | Utilize micro-nano CeO 2and ZrO 2powder doping Pb-Zn tailings prepares environment-friendly type rare earth vitrified brick |
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| CN104370524A true CN104370524A (en) | 2015-02-25 |
| CN104370524B CN104370524B (en) | 2016-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975877A (en) * | 2018-08-27 | 2018-12-11 | 西北农林科技大学 | The method of one heavy metal species slag manufacture building materials brick |
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| CN101973709A (en) * | 2010-10-28 | 2011-02-16 | 南昌航空大学 | Method for preparing calcium aluminosilicate nanometer microcrystal glass by utilizing natrium silica calcium glass waste slag |
| CN103030283A (en) * | 2012-12-05 | 2013-04-10 | 毛庆云 | Microcrystalline glass using bentonite as main material and preparation method thereof |
| CN103288354A (en) * | 2005-08-25 | 2013-09-11 | 塞拉美克斯特有限责任公司 | Synthesized hybrid rock composition, method, and article formed by the method |
| CN104071983A (en) * | 2014-07-09 | 2014-10-01 | 北京璞晶科技有限公司 | Sintering technique for producing microcrystalline glass plate from fluorite tailings |
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2014
- 2014-10-27 CN CN201410580188.1A patent/CN104370524B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288354A (en) * | 2005-08-25 | 2013-09-11 | 塞拉美克斯特有限责任公司 | Synthesized hybrid rock composition, method, and article formed by the method |
| CN101973709A (en) * | 2010-10-28 | 2011-02-16 | 南昌航空大学 | Method for preparing calcium aluminosilicate nanometer microcrystal glass by utilizing natrium silica calcium glass waste slag |
| CN103030283A (en) * | 2012-12-05 | 2013-04-10 | 毛庆云 | Microcrystalline glass using bentonite as main material and preparation method thereof |
| CN104071983A (en) * | 2014-07-09 | 2014-10-01 | 北京璞晶科技有限公司 | Sintering technique for producing microcrystalline glass plate from fluorite tailings |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975877A (en) * | 2018-08-27 | 2018-12-11 | 西北农林科技大学 | The method of one heavy metal species slag manufacture building materials brick |
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