CN104386931B - Utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker - Google Patents

Utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker Download PDF

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CN104386931B
CN104386931B CN201410589715.5A CN201410589715A CN104386931B CN 104386931 B CN104386931 B CN 104386931B CN 201410589715 A CN201410589715 A CN 201410589715A CN 104386931 B CN104386931 B CN 104386931B
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tailings
oyster shell
clinker
heavy metals
curing agent
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CN104386931A (en
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于岩
张复伟
李冲
许亚丽
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Fuzhou University
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Fuzhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The invention provides a kind of method of utilizing oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker, taking Pb-Zn tailings, oyster shell and curing agent as raw material, by oyster shell in ball mill after ball grinds, add curing agent, Pb-Zn tailings and water to carry out mix, after mixing, the section of being pressed into, after preheating and calcining, be cooled to room temperature, obtain rare-earth type heavy metals immobilization clinker. The rare-earth type heavy metals immobilization clinker that the present invention makes can reduce sintering temperature, plays energy-conserving action, can effectively solidify the heavy metal ion in Pb-Zn tailings simultaneously, has realized twice laid. Its preparation method is simple, with low cost, has good economic benefit and environmental benefit, can be produced by scale of input well.

Description

Utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker
Technical field
The invention belongs to environment and Material Field, be specifically related to one and utilize oyster shell and Pb-Zn tailings to prepare rare-earth type weightThe method of metal-cured clinker.
Background technology
Pb-Zn tailings is to produce in plumbous zinc ore ore dressing separation operation, accounts for 95% left and right of plumbous zinc ore output, a large amount of tailsOre deposit the other side not only will take soil in large quantities, and expend and deposit in large quantities and administrative expenses, the poisonous and harmful substance in mine tailing simultaneously,After weathering and rain, can there is Transport And Transformation in heavy metal particularly, and the ecological environment of periphery is produced to unrepairableDestruction. Therefore scientifically recycle resource of tailings, turn waste into wealth, accomplish two harvests of environmental benefit and economic benefitFor a kind of selection of the best. And hoarded a large amount of discarded oyster shells in the oyster bed of China coast, it has widelyAvailability and cheap cost, chemistry and Micro-Structure Analysis demonstration, it is mainly calcium carbonate and a small amount of that the one-tenth of oyster shell is grouped intoImpurity is good calcium carbonate source.
At present, have and studied the production that Pb-Zn tailings is applied to clinker, but in these recoverying and utilizing methodsThe heavy metal substance in mine tailing is not processed especially, just set it as simply a kind of raw material and use, thisSample can not solve well heavy metal substance Transport And Transformation and then environment be produced to the problem of polluting. Extract in land for growing field crops, Sanming CitySample detection result show, its main component and raw material clay raw material used approaches, and also contains a certain amount of iron simultaneouslyMatter oxide and trace element, can be used to all replace clay raw material and ferro-controlling raw material.
The clinker that has mixed rare earth element burns till above at 1350 DEG C, can promote the formation in A ore deposit, increases silicatePhase content, reduces the free calcium oxide in grog, improves burn-ability. Can reduce the temperature that in grog, liquid phase occurs, increase simultaneouslyAdd amount of liquid phase, promote Al in A ore deposit2O3And Fe2O3Solid solution, improves the hydration activity in A ore deposit. And the defect that can increase lattice, addsThe asymmetric key element of acute lattice, improves the hardness of mineral, and then improves the quality of clinker.
Due to CeO2And ZrO2At high temperature can react with some heavy metals, produce constitutionally stable soluble solids, Neng GouyouEffect ground reduces the Heavy metals problem in the process of firing and using, at the Pb to raw material and in the grog just having dispatched from the factory, CdAfter contrasting and detect with the heavy metal ion such as Zn, find to the curing degree of the heavy metals such as Pb, Cd and Zn reached respectively 56%,68% and 73%, do not add CeO2And ZrO2Before, heavy metals immobilization rate has increased significantly.
Simultaneously due to nano Ce O2Middle Ce3+And Ce4+Between reversible transition process be accompanied by generation and the elimination of oxygen vacancies, because ofAnd there is fabulous storage oxygen and the ability of oxygen release, simple CeO2Structural stability poor, and cannot meet at lower temperatureThe demand of lower catalytic oxidation, but as the CeO doped with metal ion2And ZrO2While forming solid solution, due to lattice deformity and surperficialDefect, can cause CeO2And ZrO2Catalytic performance at a lower temperature, so can be to airborne CO, nitrogen oxide andSome organic contamination deposits yields catalyticing decomposition actions such as benzene class material, produce positive effect to air cleaning. By this heavyMetal-cured technology, we successfully prepare a kind of rare-earth type heavy metals immobilization clinker.
Through retrieval, at home and abroad there is no and utilize taking Pb-Zn tailings and oyster shell as raw material, with CeO2And ZrO2For curing agent,Prepare a kind of method of rare-earth type heavy metals immobilization clinker, this project belongs to the technology of first research invention both at home and abroad. ThisInvent related main raw material(s) (Pb-Zn tailings) abundant at China's reserves, the preparation method that uses is simple and be easy to behaviourDo, can recycle the discarded object of Pb-Zn tailings and oyster shell, effectively solve the problem of mine tailing heavy metal pollution, economic effectBenefit is aobvious and environmental benefit is outstanding, has good application value.
Summary of the invention
The object of the present invention is to provide one to utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization cementThe method of grog, the rare-earth type heavy metals immobilization clinker making can reduce sintering temperature, has played energy-conservation effect, withTime can effectively solidify the heavy metal ion in Pb-Zn tailings, realized twice laid. Its preparation method is simple, and cost is lowHonest and clean, there is 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:
A kind ofly utilize rare-earth type heavy metals immobilization clinker prepared by oyster shell and Pb-Zn tailings to comprise following raw material: leadZinc mine tailing 31 ~ 34wt%, oyster shell 65.5 ~ 68.5wt%, curing agent 0.5wt%.
Described curing agent is CeO2And ZrO2, wherein CeO260~70wt%，ZrO230~40wt%。
A kind of method of utilizing oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker as above:By oyster shell ball grinds, add curing agent, Pb-Zn tailings and water to carry out mix, after mixing, repressed one-tenth section, preheating andAfter calcining, be cooled to room temperature, obtain rare-earth type heavy metals immobilization clinker.
Concrete steps are as follows:
(1) oyster shell ball milling 2h in ball mill is made to oyster shell powder;
(2) in the water of Pb-Zn tailings, oyster shell and curing agent gross mass 20%, add curing agent, stir after 30 minutes, thenAdd Pb-Zn tailings and oyster shell powder, stir, make raw material;
(3), by after the raw material section of being pressed into, preheating 1h in the stove of 900 DEG C, is warming up to 1350 DEG C of sintering 1h, comes out of the stove coolingTo room temperature, obtain rare-earth type heavy metals immobilization clinker.
The high strength rare earth clinker of the environment-friendly type that this method is prepared, the cement of measuring according to Chinese cement centre of developmentBurnability of raw material grading standard (by the f-CaO content of 1400 DEG C), its raw-meal ingredient scheme burn-ability valency level is B level, andAnd burning till in order of grog, crystallization degree is also better, and proportion of composing is comparatively reasonable. Press GB1/7671-1999 " cement mortarStrength detecting method (ISO) " the compression strength result of testing its 28d shows the standard of 62.5R of having reached. Soak according to solid wasteGo out toxicity test method (HJ/T299-2007) sample is carried out to Leaching experiment, by ICP method, goods are carried out to heavy metal moltenArtificial situation detects, and heavy metal ion leaching concentration meets GB5085.3-2007 " hazardous waste judging standard-LeachingDifferentiate ", even the concentration of part heavy metal ion has reached I class water in GB3838-2002 " water environment quality standard " and has wantedAsk, heavy metal ion leaching concentration is much smaller than the leaching concentration of Pb-Zn tailings rare earth fired brick that does not add curing agent. This is describedThe method that kind utilizes oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker has overcome tradition and has utilized in methodDeficiency, in reducing the sintering temperature of cement, when improving burn-ability, can also solidify heavy metal in discarded object fromSon, reduces and has even stopped Heavy metals that cement in use causes because of the acid rain corrosion destruction to environment. Except thisOutside, the curing agent in rare earth clinker with mine tailing in metal ion and nonmetallic ion reaction after the solid solution that producesBody, can also the harmful organic pollution of catalytic decomposition part, can be applied to the improvement field of pollutant. If can be in large quantitiesPromote the use of, will produce active influence to environment. And its preparation method is simple, with low cost, there is good warpJi benefit, can be produced by scale of input well.
Remarkable advantage of the present invention is:
(1) raw material and technological innovation: taking Pb-Zn tailings and oyster shell as raw material, with CeO2And ZrO2As curing agent, havingEffect control heavy metal substance losing issue time, the effect of also having played mineralizer has improved burnability of raw material, has promotedThe intensity of cement. Meanwhile, air cleaning is produced to positive effect, be applied to the field of Environment Protection such as sewage disposal, air cleaning.Its method is simple, has very strong operability, can be promoted and produce.
(2), through retrieval, at home and abroad there is no that to utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization cement ripeThe report of material, this project belongs to the technology of first research invention both at home and abroad.
(3) low production cost: main raw material(s) is Pb-Zn tailings and oyster shell, and it results from mining and fishery in a large numberIn the process of producing, be easy to obtain, cost is very low, and economic benefit is very remarkable, has very by force fixed market competition ability.
Detailed description of the invention
The weight proportion of composition of raw materials is: Pb-Zn tailings 31 ~ 34wt%, oyster shell 65.5 ~ 68.5wt%, curing agent0.5wt%。
The preparation method that utilization utilizes oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker specifically walksSuddenly be:
(1) oyster shell ball milling 2h in ball mill is made to oyster powder;
(2) curing agent is joined in the water of raw material gross mass 20%, stir after 30 minutes, make the suspension of curing agent;
(3) suspension added to Pb-Zn tailings and oyster shell powder and stir;
(4) after the raw material section of being pressed into, pre-burning 1h in the stove of 900 DEG C;
(5) temperature is increased to the sintering temperature insulation 1h of 1350 DEG C;
(6) come out of the stove and be cooled to the rare-earth type heavy metals immobilization clinker grog that obtains us after room temperature.
Embodiment 1
The weight proportion of composition of raw materials: Pb-Zn tailings 31%, oyster shell 68.5wt%, curing agent 0.5wt%(CeO260wt%，ZrO240wt%), by formula, three kinds of raw materials are weighed, oyster shell ball milling 2h in ball mill is made to oyster powder, by curing agentJoin in the water of raw material gross mass 20%, stir after 30 minutes, then add Pb-Zn tailings and oyster shell powder to stir, willAfter the raw material section of being pressed into, preheating 1h in the stove of 900 DEG C, at the sintering temperature insulation 1h that temperature is increased to 1350 DEG C, goes outStove is cooled to the rare-earth type heavy metals immobilization clinker grog that obtains us after room temperature.
According to GB1346-77, while measuring the initial set of its mine tailing portland cement of calcination gained at 1350 DEG C and final setBetween, by GB1/7671-1999 " strength of cement mortar detection method (ISO) ", test mine tailing cement is at the pressure resistance in the different length of timesDegree, result is as shown in table 1-1. According to solid waste Leaching assay method (HJ/T299-2007), goods are leachedToxicity test, detects leaching ability of heavy metal situation by ICP method, result as shown in table 1-2, heavy metal ion leaching concentration symbolClose GB5085.3-2007 " hazardous waste judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion has reachedI class water requirement in GB3838-2002 " water environment quality standard ".
The physical properties of table 1-1 sample
Table 1-2 clinker leaching liquor analysis result (mg/L)
Embodiment 2
The weight proportion of composition of raw materials: Pb-Zn tailings 32wt%, oyster shell 67.5wt%, curing agent 0.5wt%（CeO260wt%，ZrO240wt%), by formula, three kinds of raw materials are weighed, oyster shell ball milling 2h in ball mill is made to ostreae testa pulverataEnd, joins curing agent in the water of raw material gross mass 20%, stirs after 30 minutes, then adds Pb-Zn tailings and oyster shell powderStir, by after the raw material section of being pressed into, preheating 1h in the stove of 900 DEG C, in the sintering temperature that temperature is increased to 1350 DEG CDegree insulation 1h, comes out of the stove and is cooled to the rare-earth type heavy metals immobilization clinker that obtains us after room temperature.
According to GB1346-77, while measuring the initial set of its mine tailing portland cement of calcination gained at 1350 DEG C and final setBetween, by GB1/7671-1999 " strength of cement mortar detection method (ISO) ", test mine tailing cement is at the pressure resistance in the different length of timesDegree, result is as shown in table 2-1. According to solid waste Leaching assay method (HJ/T299-2007), goods are leachedToxicity test, detects leaching ability of heavy metal situation by ICP method, result as shown in table 2-2, heavy metal ion leaching concentration symbolClose GB5085.3-2007 " hazardous waste judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion has reachedI class water requirement in GB3838-2002 " water environment quality standard ".
The physical properties of table 2-1 sample
Table 2-2 clinker leaching liquor analysis result (mg/L)
Embodiment 3
The weight proportion of composition of raw materials: Pb-Zn tailings 33wt%, oyster shell 66.5wt%, curing agent 0.5wt%（CeO260wt%，ZrO240wt%), by formula, three kinds of raw materials are weighed, oyster shell ball milling 2h in ball mill is made to ostreae testa pulverataEnd, joins curing agent in the water of raw material gross mass 20%, stirs after 30 minutes, then adds Pb-Zn tailings and oyster shell powderStir, by after the raw material section of being pressed into, preheating 1h in the stove of 900 DEG C, in the sintering temperature that temperature is increased to 1350 DEG CDegree insulation 1h, comes out of the stove and is cooled to the rare-earth type heavy metals immobilization clinker that obtains us after room temperature.
According to GB1346-77, while measuring the initial set of its mine tailing portland cement of calcination gained at 1350 DEG C and final setBetween, by GB1/7671-1999 " strength of cement mortar detection method (ISO) ", test mine tailing cement is at the pressure resistance in the different length of timesDegree, result is as shown in table 3-1. According to solid waste Leaching assay method (HJ/T299-2007), goods are leachedToxicity test, detects leaching ability of heavy metal situation by ICP method, result as shown in table 3-2, heavy metal ion leaching concentration symbolClose GB5085.3-2007 " hazardous waste judging standard-leaching characteristic identification ", even the concentration of part heavy metal ion has reachedI class water requirement in GB3838-2002 " water environment quality standard ".
The physical properties of table 3-1 sample
Table 3-2 clinker leaching liquor analysis result (mg/L)
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change withModify, all should belong to covering scope of the present invention.

Claims (3)

1. a rare-earth type heavy metals immobilization clinker that utilizes oyster shell and Pb-Zn tailings to prepare, is characterized in that: compriseFollowing raw material: Pb-Zn tailings 31 ~ 34wt%, oyster shell 65.5 ~ 68.5wt%, curing agent 0.5wt%; Described curing agent is CeO2And ZrO2, CeO in curing agent260~70wt%，ZrO230~40wt%。
2. one kind is utilized oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker as claimed in claim 1Method, is characterized in that: by oyster shell ball grinds, add curing agent, Pb-Zn tailings and water to carry out mix, and after mixing,After repressed one-tenth section, preheating and calcining, be cooled to room temperature, obtain rare-earth type heavy metals immobilization clinker.
3. method according to claim 2, is characterized in that: concrete steps are as follows:
(1) oyster shell ball milling 2h in ball mill is made to oyster shell powder;
(2) in the water of Pb-Zn tailings, oyster shell and curing agent gross mass 20%, add curing agent, stir after 30 minutes, then addPb-Zn tailings and oyster shell powder, stir, and makes raw material;
(3), by after the raw material section of being pressed into, preheating 1h in the stove of 900 DEG C, is warming up to 1350 DEG C of sintering 1h, comes out of the stove and is cooled to chamberWen Hou, obtains rare-earth type heavy metals immobilization clinker.
CN201410589715.5A 2014-10-27 2014-10-27 Utilize oyster shell and Pb-Zn tailings to prepare rare-earth type heavy metals immobilization clinker Active CN104386931B (en)

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CN108906872A (en) * 2018-06-05 2018-11-30 杭州电子科技大学 The method for administering waste water and heavy metal pollution of soil with calcining oyster shell powder
CN113149479A (en) * 2021-03-11 2021-07-23 江西理工大学 Heavy metal curing agent for resource utilization of tungsten tailings and curing method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628751A (en) * 2009-08-10 2010-01-20 福州大学 Recyclable waste water dephosphorization material of oyster shells prepared by fire-free method and preparation method thereof
CN101830652A (en) * 2010-06-11 2010-09-15 福州大学 Method for preparing concrete admixture by utilizing oyster shells and applications
CN102786240A (en) * 2011-05-20 2012-11-21 中国科学院广州地球化学研究所 Resource treatment method for tailings by preparing cement from copper tailings
CN103524105A (en) * 2013-10-12 2014-01-22 东山县金石混凝土有限公司 Green and environment-friendly brick for building and making technology thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628751A (en) * 2009-08-10 2010-01-20 福州大学 Recyclable waste water dephosphorization material of oyster shells prepared by fire-free method and preparation method thereof
CN101830652A (en) * 2010-06-11 2010-09-15 福州大学 Method for preparing concrete admixture by utilizing oyster shells and applications
CN102786240A (en) * 2011-05-20 2012-11-21 中国科学院广州地球化学研究所 Resource treatment method for tailings by preparing cement from copper tailings
CN103524105A (en) * 2013-10-12 2014-01-22 东山县金石混凝土有限公司 Green and environment-friendly brick for building and making technology thereof

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