CN105060780B - Radiation shield concrete with nickel slag and Pb-Zn tailings as raw material and preparation method thereof - Google Patents

Radiation shield concrete with nickel slag and Pb-Zn tailings as raw material and preparation method thereof Download PDF

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CN105060780B
CN105060780B CN201510441111.0A CN201510441111A CN105060780B CN 105060780 B CN105060780 B CN 105060780B CN 201510441111 A CN201510441111 A CN 201510441111A CN 105060780 B CN105060780 B CN 105060780B
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tailings
nickel slag
raw material
radiation shield
concrete
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CN105060780A (en
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于岩
李冲
邱常睿
何亚军
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Fuzhou University
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Fuzhou University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The invention belongs to environment and architecture Material Field, and in particular to a kind of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material and preparation method thereof.Specifically include the raw material of following weight portion:The weight portion of water 150 ~ 190, the weight portion of Binder Materials 350 ~ 640, the weight portion of fine aggregate 740 ~ 850, the weight portion of coarse aggregate 1100 ~ 1700, the weight portion of water reducer 2.1 ~ 8.0, the weight portion of steel fibre 30 ~ 75;Wherein, the Binder Materials is made up of cement and mineral admixture;Described coarse aggregate is made up of Pb-Zn tailings, nickel slag and barite;Described fine aggregate is the compound of Pb-Zn tailings and nickel the slag gained after ball milling;Described water reducer is polycarboxylic acid series high efficiency water reducing agent.The radiation shield concrete low cost for being obtained, can be good at shielding α, β, gamma-rays and neutron ray, cracking resistance and superior in durability, while reducing mine tailing and nickel slag muck is rivals in a contest the pollution that ecological environment causes, with good economic benefit and environmental benefit, application prospect is good.

Description

Radiation shield concrete with nickel slag and Pb-Zn tailings as raw material and preparation method thereof
Technical field
The invention belongs to environment and architecture Material Field, and in particular to a kind of anti-spoke with nickel slag and Pb-Zn tailings as raw material Penetrate concrete and preparation method thereof.
Background technology
Nickel slag is a kind of solid slag of generation in metallic nickel and nickel alloy smelting process, i.e., its high-temperature molten is through water quenching A kind of granulated slag for being formed afterwards, wherein SiO2Content 30% -50%, Fe2O3Content 30%-60%, CaO content 1.5%-5%, MgO Content 1% -15%, Al2O3Content 2.5%-6%.Its melting behaviors is with FeO-SiO2Based on, wherein CaO, MgO and Al2O3Content is low very It is many, but SiO2And Fe2O3Content is much higher.FeO in nickel slag amorphous phase is also a kind of active component, the meeting in the presence of alkali Generation Fe (OH)2With Fe (OH)3Gel, being filled in other hydrated products can play a part of support frame, therefore can be as Aggregate produces concrete.The direct discharge of nickel slag can cause very big hidden danger to environment, allow it as the replacement of aggregate in concrete Product can well solve the problems, such as that nickel slag muck is accumulated, and can also solve the random mining pair of natural sand resource exhaustion, natural sand The destruction problem of ecological environment.
Pb-Zn tailings are waste residue of the Pb-Zn deposits factory using discharge after floatation ore dressing, and it accounts for the 95% of Pb-Zn tailings yield, and Substantial amounts of mine tailing is stacked and not only wants land occupation, expends storage and administration fee, while the harmful substance in mine tailing, particularly weighs Metal ion is after weathering and rain leaching, it may occur that release is caused sternly with migration, the life to surrounding enviroment and the people The influence and threat of weight.China's Pb-Zn tailings and its smeltery's distribution are very wide, and waste sludge discharge amount is also very big, scientifically recycles Resource of tailings, turns waste into wealth, and accomplishes the doulbe-sides' victory of environmental benefit and economic benefit and turns into a kind of optimal selection.
Nuclear technology has just rapidly been developed since the birth, but its security is always to perplex its further development It is crucial.It is well known that a large amount of such as α, β, gamma-rays and neutron rays that nuclear reaction is produced can induce cancer, leukaemia The genetic mutation of various mankind's incurable diseases and inducing plant, the growth for harming the crops, and also its incubation period is long, nothing in the short time Method is learnt.Therefore, to prevent injury of the ray to human body, when the building of radiation source is built with, it is necessary to which protection body is set.
Concrete is current the most widely used ray protection material, be mainly used in making the inside and outside shell of nuclear reactor with And the curing process of nuke rubbish.Radiation shield concrete is as atomic reactor, particle accelerator and containing the anti-of radiation source device Protective material, it can effectively shield nuclear radiation, i.e. ray, refer generally to the rays such as α, β, γ and neutron irradiation.In radiation proof In Concrete Design, the larger natural crystal of some apparent densities:Barite, serpentine etc., by its excellent alpha ray shield Performance, is commonly used as the coarse-fine aggregate of concrete.These natural crystals by its have larger atomic number and Apparent density higher, can effectively stop ray penetrating in concrete.However, these natural crystals are non-renewable , with developing rapidly for nuclear power, from the angle of sustainable development for, find alternative material significant.
On the one hand, the aggregate used by radiation shield concrete has limonite (2Fe2O3•3H2O), bloodstone (Fe2O3), magnetic iron ore (Fe3O4), barite (BaSO4), scrap iron block, iron sand or steel sand etc., quartz sand is frequently as fine aggregate.Iron-holder is more than in nickel slag 50% and other heavy metals, meet the requirement of the coarse aggregate of radiation shield concrete, there is radiation proof, anti-microwave work(for preparing The concrete of energy is highly beneficial.Meanwhile, the constituent of nickel slag and Pb-Zn tailings is mainly SiO2, CaO, Fe2O3, Al2O3, MgO Deng, can be very good to replace the materials such as quartz sand as the fine aggregate of concrete, reduce preparation cost.In addition, lead zinc tail Containing substantial amounts of heavy metals such as lead in ore deposit, because its structural arrangement is tight, density big, can well prevent ray from passing through, So that having the performance of preferably shielding ray using concrete prepared by nickel slag and Pb-Zn tailings.
On the other hand, the apparent density of nickel slag(2.6~3.2×103kg/m3)And the apparent density of Pb-Zn tailings(2.5~ 3.1×103kg/m3)With the apparent density of coagulation soil matrix phase cement mortar(2.6~3.0×103kg/m3)It is close, so that mixed Cement slurry and aggregate is well mixed in solidifying soil preparation process, reduces because structure lacks caused by concrete uniformity is bad Fall into so that the ability enhancing of concrete shield ray.Therefore, we using nickel slag and Pb-Zn tailings come processability more preferably, into This lower radiation shield concrete.
Through retrieval, at home and abroad there is no using nickel slag and Pb-Zn tailings to prepare the report of high-performance radiation shield concrete, The project belongs to the technology of first research invention both at home and abroad.Nickel slag involved in the present invention and Pb-Zn tailings in China's reserves very It is abundant, nickel slag and Pb-Zn tailings can be sufficiently recycled, efficiently solve discarded object and pile up brought pollution problem, together When due in nickel slag contain substantial amounts of Fe and other heavy metal elements, and in Pb-Zn tailings containing numerous heavy metal elements especially Pb, institute is in case ray performance is more superior.Therefore, have great importance from the point of view of economy and environment double angle, with very Good application value.
The content of the invention
It is an object of the invention to provide a kind of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material and its preparation side Method.Obtained radiation shield concrete can preferably shield α, β, gamma-rays and neutron and penetrate than other radiation shield concrete products Line, cracking resistance and superior in durability with shielding properties and concrete very high.The preparation method is simple, is adopted Nickel slag and Pb-Zn tailings can replace natural crystal as aggregate, with low cost, with good economic benefit and environment Benefit, application prospect is good.
To achieve the above object, the present invention is adopted the following technical scheme that:
A kind of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material, in parts by weight, including following raw material:Water 150 ~ 190 parts, 350 ~ 640 parts of Binder Materials, 740 ~ 850 parts of fine aggregate, 1100 ~ 1700 parts of coarse aggregate, water reducer 2.1 ~ 8.0 Part, 30 ~ 75 parts of steel fibre;Described coarse aggregate is made up of Pb-Zn tailings, nickel slag and barite.
In described coarse aggregate, mixing with mass ratio for Pb-Zn tailings, nickel slag and barite is 1:(0.2~2.5): (0.2~1.0).
Described fine aggregate is after being mixed by Pb-Zn tailings and nickel slag, by ball milling 2h, the mixing crossed obtained by 300 mesh sieves Material, wherein, Pb-Zn tailings and mixing with mass ratio for nickel slag are 1:(0.2~2.5).
Described Pb-Zn tailings include following component:SiO250 ~ 55 wt %, CaO 15 ~ 23 wt %, Fe2O3 13~18 Wt %, Al2O310 ~ 15 0.81 ~ 1.86 0.40 ~ 0.86 0.44 ~ 0.52 wt % of wt %, BaO of wt %, ZnO of wt %, PbO;
Described nickel cinder ladle includes following component:SiO230 ~ 50 wt %, Fe2O330 ~ 60 1.5 ~ 5 wt of wt %, CaO %, Al2O32.5 ~ 63 ~ 6 wt % of wt %, NiO.
Described water reducer is polycarboxylic acid series high efficiency water reducing agent.
Described Binder Materials its raw material composition is:The cement of 150 ~ 300 weight portions, the silicon ash of 20 ~ 50 weight portions and 30 ~ The flyash of 60 weight portions.
Described cement is 42.5 grades of Portland cements.
A kind of a kind of preparation method of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material as described above, specifically Step is as follows:
(1)By Binder Materials, coarse aggregate, fine aggregate and steel fibre according to proportioning add concrete mixer in, machinery 2 ~ 3min of stirring, compound is obtained after stirring;
(2)To step(1)Water reducer and water, 2 ~ 3min of mechanical agitation is proportionally added to stir in the compound of middle gained Mixture paste is obtained after mixing uniformly, mixture paste injection mould is carried out into shaping of vibrating, maintenance obtains final product radiation shield concrete.
Radiation shield concrete prepared by the present invention, its radiation proof function is mainly based upon aggregate shielding property:
Aggregate employed in radiation shield concrete preparation process is the mixing compounded by nickel slag and Pb-Zn tailings Material, contains many heavy metal elements, such as in nickel slag and Pb-Zn tailings:Mg, Ti, Co etc. so that heavy metal contains in folk prescription concrete Amount increases;Especially in nickel slag containing in the Fe and Pb-Zn tailings for having more than 50% containing more Pb, the collaboration of both raw materials Effect so that the radiation protection ability of concrete is significantly increased.When radiation source radiates α, β, γ and neutron ray, aggregate first In the relative atomic mass that contains heavy metal element high can effectively attenuation ray spread speed so as to little by little absorb Radiation ray;Secondly, inside concrete also has more chemical combination combination water, including:Free water, the crystallization water, these moisture for The absorption of the slowing down and slow neutron of fast neutron has good effect, and will not produce Secondary radiation.Meanwhile, nickel slag and lead zinc tail There is solid phase reaction in the silicoaluminate in ore deposit, make heavy metals immobilization in the crystalline substance of silicoaluminate after cement and water is added Without dissolution in lattice, it is ensured that prepare environment amenable radiation shield concrete.
This method be using aggregate nickel slag and Pb-Zn tailings compound, the table of its apparent density and Binder Materials matrix See density to approach, obvious aggregate sinkage will not be produced in concrete so that the degeee of stratification of concrete is dropped It is low, the good concrete of homogeneity is prepared, the concrete can be effectively reduced tearing tendency and the microdefect of concrete, So that aggregate is evenly distributed, durability strengthens, so as to improve the shielding properties of radiation shield concrete.
Beneficial effects of the present invention:
(1)The delamination degree of high-performance radiation shield concrete prepared by the present invention has obtained greatly reducing so that concrete Strength character and endurance quality strengthen;
(2)The present invention uses the compound of nickel slag and Pb-Zn tailings as the raw material of coarse-fine aggregate, can both be contained using it There is heavy metal element to prepare shielding properties radiation shield concrete high, α, β, gamma-rays and neutron ray shielded well, Can turn waste into wealth, solve slag, mine tailing and pile up brought environmental problem;
(3)The present invention prepares the process is simple of high-performance radiation shield concrete, raw material sources using nickel slag and Pb-Zn tailings Abundant, with low cost, application prospect is extensive.
Specific embodiment
For a better understanding of the present invention, with reference to the following examples content that the present invention is furture elucidated, but this hair It is bright to be not limited solely to the following examples.
Embodiment 1
Raw material is chosen according to the raw material proportioning in table 1, Binder Materials, coarse aggregate, fine aggregate, steel fibre are added to coagulation In native mixer, dry mixing 2min adds water reducer and water, continues to stir 3min, and mixture paste is obtained after stirring, will Mixture paste injection mould carries out shaping of vibrating, and maintenance obtains final product radiation shield concrete.Its physical property technical indicator, linearly decline Subtract coefficient and heavy metal ion leaches index and is listed in table 4, table 5 and table 6.
The embodiment 1 of table 1 prepares each material fiting ratio of radiation shield concrete
Wherein cement is 42.5 grades of Portland cement;Fine coal gray density is 0.7g/cm3;The density of silicon ash is 2.1g/cm3~2.3g/cm3;Fine aggregate is nickel slag and Pb-Zn tailings by ball milling 2h, the compound crossed obtained by 300 mesh sieves;Slightly Aggregate is the mixture of Pb-Zn tailings, nickel slag and barite, and mixing with mass ratio for Pb-Zn tailings, nickel slag and barite is 1: 1.5:0.5;Fine aggregate is the mixture of Pb-Zn tailings and nickel slag, and Pb-Zn tailings and mixing with mass ratio for nickel slag are 1:1.5;Diminishing Agent is polycarboxylic acid series high efficiency water reducing agent.
Embodiment 2
Raw material is chosen according to the raw material proportioning in table 2, Binder Materials, coarse aggregate, fine aggregate, steel fibre are added to coagulation In native mixer, dry mixing 3min adds water reducer and water, continues to stir 2min, and mixture paste is obtained after stirring, will Mixture paste injection mould carries out shaping of vibrating, and maintenance obtains final product radiation shield concrete.Its physical property technical indicator, linearly decline Subtract coefficient and heavy metal ion leaches index and is listed in table 4, table 5 and table 6.
The embodiment 2 of table 2 prepares each material fiting ratio of radiation shield concrete
Wherein cement is 42.5 grades of Portland cement;Fine coal gray density is 0.7g/cm3;The density of silicon ash is 2.1g/cm3~2.3g/cm3;Fine aggregate is nickel slag and Pb-Zn tailings by ball milling 2h, the compound crossed obtained by 300 mesh sieves;Slightly Aggregate is the mixture of Pb-Zn tailings, nickel slag and barite, and mixing with mass ratio for Pb-Zn tailings, nickel slag and barite is 1: 1:1;Fine aggregate is the mixture of Pb-Zn tailings and nickel slag, and Pb-Zn tailings and mixing with mass ratio for nickel slag are 1:1;Water reducer is poly- High Efficient Diswater.
Embodiment 3
Raw material is chosen according to the raw material proportioning in table 3, Binder Materials, coarse aggregate, fine aggregate, steel fibre are added to coagulation In native mixer, dry mixing 3min adds water reducer and water, continues to stir 2min, and mixture paste is obtained after stirring, will Mixture paste injection mould carries out shaping of vibrating, and maintenance obtains final product radiation shield concrete.Its physical property technical indicator, linearly decline Subtract coefficient and heavy metal ion leaches index and is listed in table 4, table 5 and table 6.
The embodiment 3 of table 3 prepares each material fiting ratio of radiation shield concrete
Wherein cement is 42.5 grades of Portland cement;Fine coal gray density is 0.7g/cm3;The density of silicon ash is 2.1g/cm3~2.3g/cm3;Fine aggregate is nickel slag and Pb-Zn tailings by ball milling 2h, the compound crossed obtained by 300 mesh sieves;Slightly Aggregate is the mixture of Pb-Zn tailings, nickel slag and barite, and mixing with mass ratio for Pb-Zn tailings, nickel slag and barite is 1: 0.5:2;Fine aggregate is the mixture of Pb-Zn tailings and nickel slag, and Pb-Zn tailings and mixing with mass ratio for nickel slag are 1:0.5;Water reducer It is polycarboxylic acid series high efficiency water reducing agent.
The physical property technical indicator of the radiation shield concrete of 4 embodiment of table 1 ~ 3
Table 4 illustrates that the radiation shield concrete items physical prepared by the inventive method is functional, and homogeneity is high, With good service behaviour.
The linear attenuation coefficient of the radiation shield concrete of 5 embodiment of table 1 ~ 3(cm-1
(* :Neutron data A.S.MAKARIOUS, I.I.BASHTERZ, A.EL-SAVED ABDO M.SAMIR ABDELAZIM and W.A.KANSOUH, On the utilization of heavy concrete for radiation Shielding. Ann. Nucl. Energy Vol.23, No.3,195-206,1996;Gamma-rays data Faculty of Science, Zagazig University, Zagazig, Egypt. calculation of radiation attention coefficients for shielding concretes. Ann. Nucl. Eherev.Vol.24, No.17, 1389-1401.1997)
Table 5 illustrates, radiation shield concrete prepared by embodiment 1 ~ 3 is linear to the gamma-rays of varying strength and neutron ray Damped expoential is significantly better than external performance indications, with good shielding property.
The radiation shield concrete heavy metal ion of 6 embodiment of table 1 ~ 3 leaches index
Table 6 illustrates that the heavy metal ion leaching concentration of the radiation shield concrete prepared by embodiment 1 ~ 3 meets GB5085.3-2007《Hazardous waste judging standard-leaching characteristic identification》Requirement.
Each specific raw material cited by the present invention, and each raw material bound, interval value, and technological parameter is upper Lower limit, interval value can realize the present invention, embodiment numerous to list herein, and it should all belong to covering scope of the invention.

Claims (5)

1. a kind of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material, it is characterised in that:In parts by weight, it is including following Raw material:150 ~ 190 parts of water, 350 ~ 640 parts of Binder Materials, 740 ~ 850 parts of fine aggregate, 1100 ~ 1700 parts of coarse aggregate, water reducer 2.1 ~ 8.0 parts, 30 ~ 75 parts of steel fibre;Described coarse aggregate is made up of Pb-Zn tailings, nickel slag and barite, wherein, lead zinc tail Mixing with mass ratio for ore deposit, nickel slag and barite is 1:0.2~2.5:0.2~1.0;Described fine aggregate be by Pb-Zn tailings and After the mixing of nickel slag, by ball milling 2h, the compound crossed obtained by 300 mesh sieves, wherein, Pb-Zn tailings and nickel slag are mixed with mass ratio It is 1:0.2~2.5;Described Pb-Zn tailings include following component:SiO250 ~ 55 wt %, CaO 15 ~ 23 wt %, Fe2O3 13 ~ 18 wt %, Al2O310 ~ 15 0.81 ~ 1.86 0.40 ~ 0.86 wt %, BaO 0.44 ~ 0.52 of wt %, ZnO of wt %, PbO wt %;Described nickel cinder ladle includes following component:SiO230 ~ 50 wt %, Fe2O330 ~ 60 1.5 ~ 5 wt % of wt %, CaO, Al2O32.5 ~ 63 ~ 6 wt % of wt %, NiO.
2. the radiation shield concrete with nickel slag and Pb-Zn tailings as raw material according to claim 1, it is characterised in that:It is described Water reducer be polycarboxylic acid series high efficiency water reducing agent.
3. the radiation shield concrete with nickel slag and Pb-Zn tailings as raw material according to claim 1, it is characterised in that:It is described Binder Materials its raw material composition be:The powder of the cement of 150 ~ 300 weight portions, the silicon ash of 20 ~ 50 weight portions and 30 ~ 60 weight portions Coal ash.
4. the radiation shield concrete with nickel slag and Pb-Zn tailings as raw material according to claim 3, it is characterised in that:It is described Cement be 42.5 grades of Portland cements.
5. a kind of preparation side of a kind of radiation shield concrete with nickel slag and Pb-Zn tailings as raw material as claimed in claim 1 Method, it is characterised in that:Comprise the following steps that:
(1)By Binder Materials, coarse aggregate, fine aggregate and steel fibre according to proportioning add concrete mixer in, mechanical agitation 2 ~ 3min, compound is obtained after stirring;
(2)To step(1)Water reducer and water are proportionally added in the compound of middle gained, 2 ~ 3min of mechanical agitation, stirring is equal Mixture paste is obtained after even, mixture paste injection mould is carried out into shaping of vibrating, maintenance obtains final product radiation shield concrete.
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CN107500677A (en) * 2017-09-29 2017-12-22 南京仙草堂生物科技有限公司 A kind of gamma ray shielding composite and preparation method thereof
CN109678405A (en) * 2019-01-23 2019-04-26 林瑞云 A kind of tailing base special concrete and preparation method thereof
CN112358208A (en) * 2020-11-10 2021-02-12 西北矿冶研究院 Proportioning and preparation method of cementing material
CN112551939A (en) * 2020-11-20 2021-03-26 福州大学 Ferronickel slag and steel slag composite powder high-grade concrete admixture and preparation method thereof
CN114014614B (en) * 2021-12-17 2023-02-07 中建商品混凝土有限公司 Radiation-proof concrete and preparation method thereof

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CN101676239A (en) * 2008-09-19 2010-03-24 湖南省第六工程有限公司 Premixed and pumped heavy concrete
CN103613332A (en) * 2013-11-15 2014-03-05 泰州中海建材有限公司 High-strength concrete of aggregate nickel-doped slag
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