CN107352825B - A kind of tailings of lead-zinc ore exciting agent and its application - Google Patents
A kind of tailings of lead-zinc ore exciting agent and its application Download PDFInfo
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- CN107352825B CN107352825B CN201710463922.XA CN201710463922A CN107352825B CN 107352825 B CN107352825 B CN 107352825B CN 201710463922 A CN201710463922 A CN 201710463922A CN 107352825 B CN107352825 B CN 107352825B
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- zinc ore
- exciting agent
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of tailings of lead-zinc ore exciting agent and its applications.The tailings of lead-zinc ore exciting agent includes blast-furnace cinder, flyash, fluorgypsum and water-reducing agent.It also discloses a kind of tailings of lead-zinc ore exciting agent and is preparing the application in Pb-Zn deposits packing material.Exciting agent of the invention being capable of amorphous state Silicon-rich aluminum ingredient in efficient activation tailings of lead-zinc ore, on the basis of generating presoma, based on plate calcium layer, it is grown to serve as the C-A-S-H gel with gelling ability, cementitious material is generated to efficiently use solid waste, achievees the purpose that solid waste fills.
Description
Technical field
The present invention relates to a kind of tailings of lead-zinc ore exciting agent and its applications.
Background technique
It is several that tailing filling experienced barren rock dry stowing, hydraulic filling, tailing cemented filling, tailings high dense fill etc.
The development in stage.Since 60~seventies of 20th century is applied and develops tailing cemented filling technology, cementing filler is obtained
Pay attention to and unprecedented development, main cementing material have cement, high water cementing material, red mud cementing material, the alkali-activated carbonatite cementing
Material etc..Its development trend is sent out to the directions such as setting time, low cost, high intensity, easy conveying, easy to produce, simple process are shortened
Exhibition, but cement is still mine engineering and the most widely used cementitious material of underground filling.
Filling in mine material is mainly made of aggregate and cementing agent two parts, and aggregate chooses cheap available object on the spot mostly
Material, the broken processing of the nearest sorting of insufficient section, and ordinary portland cement or slag cements are selected in cementing agent overwhelming majority mine,
The materials such as a small amount of mine incorporation flyash, red mud, lime.It is not much for the dedicated cementing material suitable for filling in mine feature
See.Just mainly there are following a few class cementing materials to apply in filling at present.
(1) cement
Currently, cement used in architectural engineering and mining engineering mainly has portland cement, ordinary portland cement, mine
Slag portland cement, portland-pozzolan cement and Portland fly ash cement etc..Portland cement is still current getter
Most widely used cementing material in journey, but there are at high cost, adaptability is not strong, and the ratio of mud and cement-sand ratio adjustable extent are narrow etc. lacks
Point.
(2) high-water material
High-moisture quick-setting tailings cemented filling material (abbreviation high-water material) is that research at the beginning of the nineties at the end of the eighties is successfully new
The cementing material of type.High-water material is to be equipped with a variety of inorganic raw materials using bauxite, lime, lime stone and gypsum as primary raw material
With additive etc. by the techniques such as broken, drying, ingredient, homogenizing, firing and grinding, two kinds of solid powders of manufactured first, second.
Have the characteristics that solid water ability strong, single slurry suspension and mobility is strong, setting rate is fast, gain in strength speed is fast, it can will be high
The water quick solidification of ratio is at the solid with certain bearing capacity.It is strong that its volumetric water content may be up to 70% or more, 1h solidification
It spends up to 0.5~1.0MPa, there is advantage under conditions of needing Fast Filling and consolidation.But filling process is complicated (double
Component), (800 yuan~1000 yuan/ton) at high cost, obturation has bleed phenomenon, and wide popularization and application has certain limitation.And
Later strength substantially retraction, the easy dusting of obturation.
(3) alkali-activated carbonatite cementing material
Such material is aided with inhomogeneity based on independent or compounding blast-furnace cinder, flyash, steel slag isoreactivity admixture
The alkali-activator of type, additive or (and) a small amount of natural minerals.Without calcination, equipment investment is few, simple production process, production
Cost is relatively low, and economic benefit is obvious, and due to comprehensively utilizing industrial residue, turns waste into wealth.During certain filling in mine,
In situation identical with 42.5 cement consumption of strength grade, early strength can reach 2~4 times of cement or more.Because of tailing class
Type is various, and the excitation system of such material is not unique, and identical material solidification tailing performance difference is larger, it is therefore desirable to needle
Dedicated experiments and research are carried out to different tailings to determine the optimal cementing system of cost performance, and swashing there is no " once and for all "
Send out agent prescription.
In addition, the size distribution situation of tailings decides the overall process of filling process, to preparation, conveying and Quality of filling body
It is of great impact.The size distribution of tailings is also referred to as the gradation of material, refers to the percentage composition of different-grain diameter particle in granular material.
By taking the tailings of all mouth Pb-Zn deposits as an example, which is mainly distributed on 5 μm~250 μm this sections and accounts for 99%, 200 mesh with
Upper particle accounts for about 43%.Compared with the tailing of other metal mines, all mouth tailings of lead-zinc ore overall fineness are moderate, fine particle content
It is fewer, all mouth Pb-Zn deposits are primarily due to using cyclone and carry out crude tailings classification processing, are classified thick tailings and are implemented filling, point
The thin tailings of grade is all discharged into Tailings Dam.This just need to tailings feature carry out system test, research and development cost performance it is high it is dedicated swash
Send out agent.
Summary of the invention
The purpose of the present invention is to provide a kind of tailings of lead-zinc ore exciting agent and its applications.
The technical solution used in the present invention is:
A kind of tailings of lead-zinc ore exciting agent, includes following components by mass parts: 90~110 parts of blast-furnace cinders, and 35~45 parts
Flyash, 6~10 parts of fluorgypsums, 0.5~1 part of water-reducing agent.
Blast-furnace cinder is conversion pig slag.
Flyash is I grade or II grade of F class flyash.
Water-reducing agent is lignin sulfonate water-reducing agent, naphthalene water reducer, melamine system water reducer, sulfamate system
Water-reducing agent, at least one of fatty acid series water-reducing agent, poly carboxylic acid series water reducer.
A kind of tailings of lead-zinc ore exciting agent is preparing the application in Pb-Zn deposits packing material.
Pb-Zn deposits packing material includes tailings of lead-zinc ore, tailings of lead-zinc ore exciting agent and water.
Tailings of lead-zinc ore exciting agent accounts for the 3~9% of Pb-Zn deposits packing material quality.
The beneficial effects of the present invention are:
Exciting agent of the invention can amorphous state Silicon-rich aluminum ingredient in efficient activation tailings of lead-zinc ore, generating forerunner
On the basis of body, based on plate calcium layer, it is grown to serve as the C-A-S-H gel with gelling ability, so that effective use is solid
It is useless to generate cementitious material, achieve the purpose that solid waste fills.
Specific embodiment
A kind of tailings of lead-zinc ore exciting agent, includes following components by mass parts: 90~110 parts of blast-furnace cinders, and 35~45 parts
Flyash, 6~10 parts of fluorgypsums, 0.5~1 part of water-reducing agent.
Preferably, a kind of tailings of lead-zinc ore exciting agent, includes following components by mass parts: 95~105 parts of blast-furnace cinders, and 37
~41 parts of flyash, 7~9 parts of fluorgypsums, 0.6~0.9 part of water-reducing agent.
Preferably, the blast-furnace cinder is conversion pig slag.
Preferably, the flyash is I grade or II grade of F class flyash；It is further preferred that the flyash is I
Grade F class flyash.
Preferably, the water-reducing agent is lignin sulfonate water-reducing agent, naphthalene water reducer, melamine series diminishing
Agent, sulfamate based water reducer, at least one of fatty acid series water-reducing agent, poly carboxylic acid series water reducer；It is further preferred that
The water-reducing agent is at least one of naphthalene water reducer, poly carboxylic acid series water reducer.
A kind of tailings of lead-zinc ore exciting agent is preparing the application in Pb-Zn deposits packing material.
Pb-Zn deposits packing material includes tailings of lead-zinc ore, tailings of lead-zinc ore exciting agent and water.
Tailings of lead-zinc ore exciting agent accounts for the 3~9% of Pb-Zn deposits packing material quality.
Further, tailings of lead-zinc ore includes following components by mass fraction: 1%~2%MgO, 7%~8%Al2O3,
21%~25%SiO2, 24%~26%SO3, 1%~2%K2O, 18%~21%CaO, 0.2%~0.4%TiO2, 15%~
18%Fe2O3, 0.3%~0.6%ZnO, 0.5%~1%PbO, surplus is loss on ignition.
Further, in the partial size of tailings of lead-zinc ore, 5 μm~50 μm account for 23~24wt%, 50 μm~75 μm account for 19~
20wt%, 75 μm~250 μm account for 55~56wt%.
Tailings exciting agent of the invention is while to be aided with activity excitation means using industrial residue as main raw material(s), is made
Can High water cut, high fineness Tailings Slurry environment in play exciting agent aquation advantage, realize the sustainable growth of intensity.
In exciting agent with two-phase Microphase Separation structure, wherein in vitreum Al-O key ratio Si-O key ratio Si-O key key
It is strong small, it is easy the agent dissolution dispersion that is excited, when the ligancy of A1 is 6, the key Qiang Geng little of alumina octahedral, about Si-O key
50% or so, activity is higher, when levigate waste residue and certain density OH-When contact, aluminum-oxygen tetrahedron and alumina octahedral are first
Dispersion is dissolved in oxygen-octahedron.In addition, Mg2+It is distributed in the hole of vitreum reticular structure, forms uneven object phase, add
The disordering arrangement of crystallite phase, is conducive to the aquation of waste residue in acute vitreum.Rich calcium phase occupies the majority in the industrial residue, for even
Continuous phase, discrete Si-rich phase is wrapped in and wherein constitutes the structure of its vitreum by it.Rich calcium phase has higher than Si-rich phase
Thermodynamic phase, while rich calcium phase has certain dynamic stability again, and being allowed to destruction must overcome certain work
Change energy.In alkaline environment, OH-Effect can overcome the decomposition activation energy of rich calcium phase, make the rapid aquation of rich calcium phase and disintegration,
Waste residue vitreous structure is caused to destroy；Si-rich phase is then gradually exposed in alkaline medium, and occur more slow aquation and
It decomposes.The hydrated product hydrated calcium silicate (C-S-H) of rich calcium phase and Si-rich phase is constantly formed and is grown up, and makes the structure of hydrated product
Constantly enhancing, show as cementitious material early period low strength and later strength constantly increases.
Above-mentioned discussion simply shows the industrial residue in exciting agent and forms bonding component aquation silicic acid under alkalinity effect
The C-S-H package tailings particles of the process of calcium (C-S-H), generation form a part of strength of filling mass.If only relying on obturation
In gelling substance, obturation short texture, low strength.If expansion component entringite can be introduced in obturation
(Ca6Al2(SO4)3(OH)12·26H2O, AFt) interstitital texture hole, tailings particles are squeezed, obturation porosity, In can be reduced
When bonding component and expansion component are coordinated to be formed, obturation can be made to be in optimum structure, intensity is best.
The contents of the present invention are described in further detail below by way of specific embodiment.
Embodiment:
Carry out filling application below in all mouth Pb-Zn deposits.
Tailings of lead-zinc ore used below includes following components by mass fraction through detecting: 1.49%MgO, and 7.97%
Al2O3, 23.28%SiO2, 25.95%SO3, 1.47%K2O, 19.28%CaO, 0.28%TiO2, 16.42%Fe2O3, 0.45%
ZnO, 0.84%PbO, 2.178% loss on ignition.In partial size, 5 μm~50 μm account for 23.64wt%, and 50 μm~75 μm account for
19.21wt%, 75 μm~250 μm account for 55.76wt%.
One, filler and filling stope prepare
1, filler prepares: Filling Station cement bin empties, and exciting agent is directly taken Filling Station.It can not such as empty,
Loading time is then calculated according to charging quantity, 20min is filled using exciting agent first, to ensure to test filling during process sampling
The all exciting agents of the invention of filling chock material.
The group of the exciting agent become 102 parts of blast-furnace cinders (conversion pig slag), 39 parts of I grade of F class flyash, 8.25 parts
Fluorgypsum, 0.75 part of naphthalene water reducer.
2, the 308 and 606-1 stope for being selected in all mouth mining areas carries out pilot scale filling.
Two, it fills cement-sand ratio and test specimen prepares
1, according to mining production requirement, in the bottoming of stope, intermediate position, the optional waterproof mortar in different cement-sand such as top position are connect
(mass ratio of tailings of lead-zinc ore exciting agent and tailings of lead-zinc ore) is filled.In application process, by adjusting filling control system
System fills cement-sand ratio according to 1:12,1:14,1:16 and 1:18 etc. four proportions and carries out filling sampling.
2, Filling density (solid content of tailings of lead-zinc ore exciting agent and tailings of lead-zinc ore) and cement-sand ratio see the table below 1.
1 Filling density of table and cement-sand ratio
3, in stowing operation, the mobile performance of Tailings Slurry in the case of waterproof mortar in different cement-sand is paid close attention to, it is ensured that filler and cement
Compared to the mobility that will not influence Tailings Slurry.
4, when filling, in the case of every kind of cement-sand ratio, 4 groups of examinations are reserved using the mold of 70.7*70.7*70.7mm in Filling Station
Part measures 7 days and 28 days compression strength respectively.
Three, test piece maintenance and strength test
1, Filling Station test piece maintenance condition considers according to following two situation, carries out the test of Hangzhoupro Compressive Strength in corresponding age.
(1) 20 ± 2 DEG C of temperature, relative humidity is not less than 60%, to simulate Underground filler ambient temperature and humidity requirement.
(2) Filling Station shaping test piece is directly taken underground cured under same condition.
2, reach predetermined age, testing crew is gone into the well to filling stope, and core boring sampling, measurement filling are carried out in obturation
The solid strength of body.
3, Filling Station keeps sample test specimen and obturation core boring sampling test specimen directly can be detected or be entrusted in Filling Station laboratory
The unit with corresponding qualification is ask to be detected.
Four, method for testing and detecting and product strength standard
1, test method
(1) quantitative Tailings Slurry and filler are put into blender by waterproof mortar in different cement-sand and mix slowly 60s；
(2) gauge water is mixed, slurry is configured to various concentration, quickly stirs 90s；
(3) after scraping pot wall surrounding slurry in pot, it is stirred for 30s；
(4) solidification sample is put into three times in steel die trial；
(5) sample is formed to after losing plasticity and is demoulded, and the actual environment for simulation underground with respect to constant temperature and humidity demoulds sample
It is placed in maintenance to test age in standard curing room and carries out intensity and volume stability test.
2, intensity detection
Intensity after tailings solidifies is much lower compared with cement and concrete, it is therefore necessary to be measured using small-range press machine
Solidify sample different larval instar single shaft Hangzhoupro Compressive Strength, compression rate 3mm/min.
Obturation test block single shaft Hangzhoupro Compressive Strength calculation formula: σ=P/A
In formula: σ is two obturation test block single shaft Hangzhoupro Compressive Strengths, and MPa-calculating takes three effective digitals；P is test block destruction
Maximum load, N；A be two perpendicular to loading direction test block area, mm2。
Test age is respectively 7 days and 28 days.
Five, using test result
The strength test results that scene connects slurry are as shown in table 2 below.
2 scene of table connects the strength test results of slurry
The laboratory in mine carries out cement and exciting agent intensity detection to field test according to the ratio simultaneously, and the results are shown in Table 3.
Craft same period test result in laboratory in 3 mine of table
Using the charging formula low strength of cement, in actual use, even if the cement-sand ratio of 1:8,28d intensity is still below
Exciting agent 1:18；Cement-sand ratio adjustability is weak, and intensity decline is obvious under low cement-sand ratio.And exciting agent can be flowed ensuring slurry
The varying strength requirement for meeting obturation under the premise of property, in 1:8~1:18 cement-sand ratio, under the same terms, using exciting agent
Sample 28d intensity is about cement solidification tailings more than 2 times, reaches cementitious material used in same intensity level and reduces about than cement
50%.
Claims (1)
1. a kind of tailings of lead-zinc ore exciting agent is preparing the application in Pb-Zn deposits packing material, it is characterised in that: Pb-Zn deposits filling
Material includes tailings of lead-zinc ore, tailings of lead-zinc ore exciting agent and water；Tailings of lead-zinc ore exciting agent accounts for Pb-Zn deposits packing material quality
3~9%；
The tailings of lead-zinc ore, includes following components by mass fraction: 1.49%MgO, 7.97%Al2O3, 23.28%SiO2,
25.95%SO3, 1.47%K2O, 19.28%CaO, 0.28%TiO2, 16.42%Fe2O3, 0.45%ZnO, 0.84%PbO,
2.178% loss on ignition；
In the partial size of the tailings of lead-zinc ore, 5 μm~50 μm account for 23.64wt%, and 50 μm~75 μm account for 19.21wt%, 75 μm~
250 μm account for 55.76wt%；
The tailings of lead-zinc ore exciting agent is composed of the following components by mass parts: 102 parts of blast-furnace cinders, 39 parts of I grade of F class fine coal
Ash, 8.25 parts of fluorgypsums, 0.75 part of naphthalene water reducer；Blast-furnace cinder is conversion pig slag.
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| CN111393121A (en) * | 2020-05-02 | 2020-07-10 | 桂林理工大学 | Method for preparing aerated concrete from lead-zinc ore smelting slag-steel slag |
| CN115215588B (en) * | 2022-06-09 | 2023-06-30 | 深圳市中金岭南有色金属股份有限公司凡口铅锌矿 | Filling material and preparation method thereof |
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| US6451104B2 (en) * | 2000-02-08 | 2002-09-17 | Rha Technology, Inc. | Method for producing a blended cementitious composition |
| CN103102089B (en) * | 2013-01-30 | 2014-11-05 | 中钢集团马鞍山矿山研究院有限公司 | Binding material for filling fine-grain tailings |
| CN103342481B (en) * | 2013-07-08 | 2016-01-13 | 武汉理工大学 | A kind of filling in mine cementitious slurry and preparation method thereof |
| CN103613294A (en) * | 2013-12-05 | 2014-03-05 | 王宗森 | Cementing material for underground filling and preparation method thereof |
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