CN110451903A - A kind of composite cementitious materials and the cementing method of the ultra-fine tailings of lead-zinc ore of high-sulfur - Google Patents
A kind of composite cementitious materials and the cementing method of the ultra-fine tailings of lead-zinc ore of high-sulfur Download PDFInfo
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- CN110451903A CN110451903A CN201910806939.XA CN201910806939A CN110451903A CN 110451903 A CN110451903 A CN 110451903A CN 201910806939 A CN201910806939 A CN 201910806939A CN 110451903 A CN110451903 A CN 110451903A
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- sulfur
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- zinc ore
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
- C04B28/082—Steelmaking slags; Converter slags
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of method that composite cementitious materials and the ultra-fine tailings of lead-zinc ore of high-sulfur are cementing, which is made of flyash, steel slag, miberal powder, desulfurized gypsum, raw lime stone, exciting agent etc..The composite cementitious materials are mainly using industrial residue as raw material, realize the purpose of the treatment of wastes with processes of wastes against one another, sufficient recycling has been carried out to resource, meet sustainable development idea, there is good Social benefit and economic benefit, and the composite cementitious materials can effectively consolidate the ultra-fine tailings of lead-zinc ore of high-sulfur, gained cementation solidifying body has the characteristics that early strength is big, stable long-term strength increases, durability is good.
Description
Technical field
The present invention relates to a kind of composite cementitious materials, in particular to a kind of cementing for high-sulfur ultra-fine grain tailings of lead-zinc ore
Composite cementitious materials, the method for further relating to high-sulfur ultra-fine grain tailings of lead-zinc ore underground consolidated fill belongs to solid waste
Processing technology field.
Background technique
Tailings is that dressing plant uses specific production technology and technology that grinde ore is therefrom extracted useful ingredient
The solid waste being discharged afterwards.During lead-zinc ore mining, with the increase of mining depth, ore taste is become
Change, mine changes ore-dressing technique, thereby result in mine for filling tailings property change, tailings particle size attenuates, and fills
Concentration reduction is filled out, Quality of filling body declines, and with deep increasing is adopted, filling pipeline increases, and pipe network system is more complicated.
In global field of mining, the method for mining by the way of filling is with a long history, is widely used, and it is dry to particularly may be divided into barren rock for filling both at home and abroad
Several stages such as formula filling, hydraulic filling, low concentration consolidated fill, highly concentrated cemented fill, paste body filling and Paste-like body filling,
Although carrying out a large amount of experimental study for tailings curing performance, achievement is a lot of, is not solved there are still individual problem
Certainly, for example, under identical cement mixing content, the cured body strength formed using thin tailings as filling aggregate is lower, and filling cost is high；
The processing technique of overflow tailings is not mature enough.The tailings particle size stored up naturally now is thinner, invades by long-term wind and rain
Erosion, contained harmful substance not only pollute air, more generate huge harm to body of groundwater.Ultra-fine grain tailings is difficult to sink
Drop using addition flocculant or need to increase the means accelerated sedimentations such as settling area, and granularity is smaller, porosity increase dehydration resistance
Increase, obturation is more difficult to be dehydrated, and it is slower to form intensity.Same slurry concentration and cement-sand ratio, the filling test block of ultra-fine grain tailings
Compression strength is far below the filling test block of common grade tailings, the especially high tailings of sulfur-bearing as filling aggregate and fills in the presence of preparation
Viscosity is higher after extender paste, is not easy the disadvantages of stirring, and causes high-sulfur ultra-fine grain tailings of lead-zinc ore that there is difficult consolidation, hardly possible to fill
Feature.For the tailings of lead-zinc ore for dissolving a large amount of high-sulfur ultra-fine grains, the solid waste treatment of wastes with processes of wastes against one another is made full use of, reaches innoxious
Processing, needs to find a kind of cementing material that can effectively consolidate high-sulfur ultra-fine grain tailings of lead-zinc ore.
Summary of the invention
The problems such as poor for the above-mentioned ultra-fine grain of high-sulfur in the prior art tailings of lead-zinc ore consolidation effect, of the invention first
A purpose is to be to provide a kind of cementing material for high-sulfur ultra-fine grain tailings of lead-zinc ore underground consolidated fill, the agglutination material
Material raw material is easy to get, is at low cost, and consolidation effect is good, can form high-intensitive, stable adhesive bond.
Second object of the present invention is to be to provide a kind of method that high-sulfur ultra-fine grain tailings of lead-zinc ore is cementing, the party
The efficient cementing of high-sulfur ultra-fine grain tailings of lead-zinc ore, the adhesive bond intensity of generation may be implemented using above-mentioned cementing material in method
It is high, stable, and cementation process is simple, can operate according to normal conditions, be conducive to large-scale application.
In order to achieve the above technical purposes, the present invention provides a kind of composite cementitious materials comprising following quality percentage
Than component: flyash 5%~25%；Steel slag 10%~30%；Miberal powder 30%~55%；Desulfurized gypsum 15%~25%；Raw stone
Ash 3%~15%；Exciting agent 1%~5%.It is 100% metering with each component gross mass.
Preferred composite cementitious materials are grouped as by following mass percent group: flyash 15%~20%；Steel slag 12%
~20%；Miberal powder 30%~45%；Desulfurized gypsum 18%~20%；Quick lime 9%~10%；Exciting agent 3%~4%.With each
Component gross mass is 100% metering.
Preferred scheme, the miberal powder are the blast furnace slag of high fineness, high activity.Miberal powder is blast furnace slag warp
Cross the process such as dry, grinding activation, obtained high fineness, high activity powder.
Preferred scheme, calcium sulphate dihydrate mass percentage content >=93% in the desulfurized gypsum.
Preferred scheme, the exciting agent include NaOH, NaCO3At least one of.
The present invention also provides a kind of method that high-sulfur ultra-fine grain tailings of lead-zinc ore is cementing, this method is by ultra-fine grain
Tailings is mixed with the composite cementitious materials and water size mixing after, form, maintenance.
Preferred scheme, the high-sulfur ultra-fine grain tailings of lead-zinc ore granularity meet quality percentage of the partial size less than 19 microns
80% or more is accounted for than content.
Preferred scheme, high-sulfur ultra-fine grain tailings of lead-zinc ore are that 1:3~7 mix by cement-sand ratio with composite cementitious materials,
It is more preferably 1:4~5.
Preferred scheme, high-sulfur ultra-fine grain tailings of lead-zinc ore mix the slurry sized mixing with composite cementitious materials and water
Concentration is 58%~65%.
Composite cementitious materials of the invention are prepared as follows to obtain:
A. flyash, steel slag, desulfurized gypsum, quick lime are mixed according to a certain percentage, is put into planetary ball mill, ball
After mill stirring 30min, ball grinding stirring 30min obtains mixture A to interval 20min again.
B. it is put into after mixture A and miberal powder, exciting agent being mixed in SM-500 test mill, ball grinding stirring 10min is obtained
To cementing material.
In composite cementitious materials of the invention, the active SiO that includes in flyash2, activity Al2O3With f-CaO (free oxygen
Change calcium) etc. be all advantageous active constituent, itself is slightly with or without hydraulic gelling property, but in the presence of with powdery and water,
It can be sent out in room temperature, especially under the conditions of hydro-thermal process or steam curing with calcium hydroxide or other alkaline earth metal hydroxides
Biochemical reaction generates the compound with hydraulic gelling property, can become a kind of material for increasing intensity and durability.Steel
Contain the tricalcium silicate (C with hydraulic gelling in slag3S), dicalcium silicate (C2S) and ferrous aluminate isoreactivity mineral, impart
Composite cementitious materials have the good characteristics such as wear-resisting, High anti bending strength, corrosion-resistant, freeze proof.Miberal powder is with blast furnace slag, warp
High fineness that is dry, obtaining after the process such as grinding, high activity powder can not only reduce the cost of composite cementitious materials, and
And good mechanical property can be made it have, the features such as volume stability is good.Desulfurized gypsum main component as the natural gypsum,
For calcium sulphate dihydrate CaSO4·2H2O, content >=93% are mainly used for adjusting the consolidation time of material.Exciting agent is NaOH, Ca
(OH)2、NaCO3Deng utilizing free OH-Basicity is provided for hydrated environment, destroys the chemical bond of the materials such as miberal powder, for recombination wound
Make adequate condition.Flyash, steel slag and miberal powder belong to potential active material, pass through its work of the excitation of quick lime and exciting agent
Property, it can guarantee that strength of filling mass steadily increases, desulfurized gypsum provides CaSO4, it generates and is conducive to gain in strength calcium sulphoaluminate,
Based on the synergistic effect of each component in composite cementitious materials, the ultra-fine tailings of lead-zinc ore surface meta-stable of high-sulfur can be allowed, and then generate
Good consolidation effect is played in complex reaction.
Compared with the prior art, technical solution of the present invention bring advantageous effects are as follows:
1. main component contains three kinds of flyash, steel slag, miberal powder waste residues in composite cementitious materials of the invention, largely disappear
It has received solid waste, has realized the resource utilization of waste residue, achieved the effect that the treatment of wastes with processes of wastes against one another, it is cementing to reduce ultra-fine grain tailings
Cost.
2. composite cementitious materials of the invention are coupled by improving tailings particles contact, reinforced structure, transition contact conversion
For same phase or it is similar be in contact, so that tailing is generated physical bond and chemical bonding in the curing process, partial size can be consolidated
80% or more ultra-fine grain tailings is accounted for less than 19 microns, and consolidation effect is good.
3. composite cementitious materials of the invention consolidate the ultra-fine tailings of lead-zinc ore of high-sulfur compared with cement cementitious material consolidation, Gu
Knotting strength is high, more can effectively solidify poisonous and harmful substance therein.
4. composite cementitious materials of the invention and the ultra-fine tailings of lead-zinc ore of high-sulfur directly adopt moulding by casting by sizing mixing
Mode is filled into mine, achievees the purpose that mine is repaired.
5, not only raw material sources are extensive, at low cost, simple production process for composite cementitious materials of the invention, but also a variety of
Solid waste, which combines, realizes efficiently comprehensive utilization ratio.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
In following embodiment:
Calcium sulphate dihydrate mass percentage content >=93% in desulfurized gypsum；
High-sulfur ultra-fine grain tailings of lead-zinc ore granularity meet mass percentage content of the partial size less than 19 microns account for 80% with
On；
Miberal powder is high fineness, high activity blast furnace slag.It is blast furnace slag by techniques such as dry, grinding activation
Processing, obtained powder.
Embodiment 1
Using following raw material by percentage to the quality: flyash 15%, blast furnace slag 35%, takes off steel slag 20%
Sulphur gypsum (CaSO4·2H2O content >=93%) 18%, quick lime 9%, sodium carbonate 3%, by flyash in above-mentioned raw materials, steel slag,
Desulfurized gypsum, quick lime are put into planetary ball mill, and interval 20min stirring twice, stirs 30min every time, and obtained is mixed
It closes object A to mix with blast furnace slag and sodium carbonate again, tests mill stirring 10min with SM-500, cementing material is made.
High-sulfur ultra-fine grain tailings of lead-zinc ore is first through broken sieving pretreatment, in the item that cement-sand ratio is 1:4 and concentration 58%
Under part, tailing, cementing material, tap water stirring are slurried, require to carry out molding in fact according to " tailing-filled experimental implementation specification "
Test, test block size 70.7mm × 70.7mm × 70.7mm conserves demoulding for 24 hours at room temperature, after constant-temperature moisture-keeping is carried out in curing box
Maintenance, maintenance to regulation age (7d, 28d), referring to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture mark
It is quasi- " measurement compression strength.
Change the range 58%~64% of slurry concentration, other conditions are consistent, and gained test block pressure resistance intensity is as follows:
The different slurry concentration experimental designs of table 1 and result
Cementing material consolidation strength as can be seen from Table 1 obtained by the present invention is high, and wherein slurry concentration can reach for 64%
To the test block of larger compression strength.
Embodiment 2
Using following raw material by percentage to the quality: flyash 15%, blast furnace slag 35%, takes off steel slag 20%
Sulphur gypsum (CaSO4·2H2O content >=93%) 18%, quick lime 9%, sodium hydroxide 3%, by flyash, steel in above-mentioned raw materials
Slag, desulfurized gypsum, quick lime are put into planetary ball mill, and interval 20min stirring twice, stirs 30min every time, obtained
Mixture A is mixed with blast furnace slag and sodium hydroxide again, tests mill stirring 10min with SM-500, cementing material is made.
High-sulfur ultra-fine grain lead-zinc ore tailings are first through broken sieving pretreatment, in the item that cement-sand ratio is 1:4 and concentration 58%
Under part, tailing, cementing material, tap water stirring are slurried, require to carry out molding in fact according to " tailing-filled experimental implementation specification "
Test, test block size 70.7mm × 70.7mm × 70.7mm conserves demoulding for 24 hours at room temperature, after constant-temperature moisture-keeping is carried out in curing box
Maintenance, maintenance to regulation age (7d, 28d), referring to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture mark
It is quasi- " measurement compression strength.
Under the conditions of waterproof mortar in different cement-sand, slurry concentration 64%, ceteris paribus, gained test block pressure resistance intensity is as follows:
Table 2 does not have to cement-sand ratio experimental design and result
Waterproof mortar in different cement-sand influences the compression strength of test block as can be seen from Table 2, and when cement-sand ratio is 1:4,28d compression strength reaches
To 4.2MPa, and intensity reduces with the reduction of cement-sand ratio.
Embodiment 3
Using following raw material by percentage to the quality: flyash 15%, blast furnace slag 35%, takes off steel slag 20%
Sulphur gypsum (CaSO4·2H2O content >=93%) 18%, quick lime 9%, sodium hydroxide 3%, by flyash, steel in above-mentioned raw materials
Slag, desulfurized gypsum, quick lime are put into planetary ball mill, and interval 20min stirring twice, stirs 30min every time, obtained
Mixture A is mixed with blast furnace slag and sodium hydroxide again, tests mill stirring 10min with SM-500, cementing material is made.
High-sulfur ultra-fine grain lead-zinc ore tailings are first through broken sieving pretreatment, in the item that cement-sand ratio is 1:4 and concentration 58%
Under part, tailing, cementing material, tap water stirring are slurried, require to carry out molding in fact according to " tailing-filled experimental implementation specification "
Test, test block size 70.7mm × 70.7mm × 70.7mm conserves demoulding for 24 hours at room temperature, after constant-temperature moisture-keeping is carried out in curing box
Maintenance, maintenance to regulation age (7d, 28d), referring to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture mark
It is quasi- " measurement compression strength.
Change the formula of cementing material, other conditions are constant, and the result of gained test block is as follows:
The design of 3 different formulations cementing material cure test of table and result
By table 3 it can be concluded that the cementing material of different formulations can reach obturation compressive strength standard in 28d in range,
5th group of experiment, which is unsatisfactory for matching obtained obturation, is unsatisfactory for intensity requirement.
The declarative knowledge of above embodiments be used to help understand the present invention, make professional and technical personnel in the field can be realized or
Using the present invention, it is not intended to limit the invention.Any modification for therefore, all within the spirits and principles of the present invention, being made,
Equivalent replacement, improvement, combination etc. should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of composite cementitious materials, it is characterised in that: including following mass percent component:
Flyash 5%~25%；
Steel slag 10%~30%；
Miberal powder 30%~55%；
Desulfurized gypsum 15%~25%；
Quick lime 3%~15%；
Exciting agent 1%~5%.
2. a kind of composite cementitious materials according to claim 1, it is characterised in that: be grouped by following mass percent group
At:
Flyash 15%~20%；
Steel slag 12%~20%；
Miberal powder 30%~45%；
Desulfurized gypsum 18%~20%；
Quick lime 9%~10%；
Exciting agent 3%~4%.
3. a kind of composite cementitious materials according to claim 1 or 2, it is characterised in that: the miberal powder is water quenching Blast Furnace Ore
Ground-slag material.
4. a kind of composite cementitious materials according to claim 1 or 2, it is characterised in that: two water sulphur in the desulfurized gypsum
Sour calcium mass percentage content >=93%.
5. a kind of composite cementitious materials according to claim 1 or 2, it is characterised in that: the exciting agent include NaOH,
NaCO3At least one of.
6. a kind of method that high-sulfur ultra-fine grain tailings of lead-zinc ore is cementing, it is characterised in that: by high-sulfur ultra-fine grain Pb-Zn deposits tail
Sand mixes after sizing mixing with the described in any item composite cementitious materials of Claims 1 to 5 and water, forms, maintenance.
7. a kind of cementing method of high-sulfur ultra-fine grain tailings of lead-zinc ore according to claim 6, it is characterised in that: described
High-sulfur ultra-fine grain tailings granularity meets mass percentage content of the partial size less than 19 microns and accounts for 80% or more.
8. a kind of cementing method of high-sulfur ultra-fine grain tailings of lead-zinc ore according to claim 6, it is characterised in that: compound
Cementing material is that 1:3~7 mix by cement-sand ratio with high-sulfur ultra-fine grain tailings of lead-zinc ore.
9. a kind of cementing method of high-sulfur ultra-fine grain tailings of lead-zinc ore according to claim 6, it is characterised in that: high-sulfur
It is 58%~65% that ultra-fine grain tailings of lead-zinc ore, which mixes the slurry concentration sized mixing with composite cementitious materials and water,.
10. a kind of cementing method of high-sulfur ultra-fine grain tailings of lead-zinc ore according to claim 6, it is characterised in that: institute
Molding is stated by the way of pouring molding.
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Cited By (9)
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| CN111170663A (en) * | 2019-12-28 | 2020-05-19 | 肇庆市武大环境技术研究院 | Sea mud curing agent |
| 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 |
| CN112408840A (en) * | 2020-11-25 | 2021-02-26 | 肇庆市武大环境技术研究院 | Curing agent for building slurry and application method thereof |
| CN112664265A (en) * | 2020-12-24 | 2021-04-16 | 安徽马钢张庄矿业有限责任公司 | Auxiliary device for cemented filling of metallurgical mine tailings and application method thereof |
| CN113526923A (en) * | 2021-05-13 | 2021-10-22 | 西北矿冶研究院 | High-sulfur iron tailing filling curing agent and preparation method thereof |
| CN114213046A (en) * | 2021-12-31 | 2022-03-22 | 徐州中矿大贝克福尔科技股份有限公司 | Clinker-free coal ash composite cementing material, preparation method thereof and coal mine filling paste |
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| CN115010458A (en) * | 2022-05-16 | 2022-09-06 | 北京安科兴业矿山安全技术研究院有限公司 | Coal mine underground filling material prepared from metal ore overflow tailings and process and application thereof |
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| CN111170663A (en) * | 2019-12-28 | 2020-05-19 | 肇庆市武大环境技术研究院 | Sea mud curing agent |
| 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 |
| CN112408840A (en) * | 2020-11-25 | 2021-02-26 | 肇庆市武大环境技术研究院 | Curing agent for building slurry and application method thereof |
| CN112664265A (en) * | 2020-12-24 | 2021-04-16 | 安徽马钢张庄矿业有限责任公司 | Auxiliary device for cemented filling of metallurgical mine tailings and application method thereof |
| CN112664265B (en) * | 2020-12-24 | 2022-11-18 | 安徽马钢张庄矿业有限责任公司 | Metallurgical mine tailing cemented filling auxiliary device and using method thereof |
| CN113526923A (en) * | 2021-05-13 | 2021-10-22 | 西北矿冶研究院 | High-sulfur iron tailing filling curing agent and preparation method thereof |
| CN114213046A (en) * | 2021-12-31 | 2022-03-22 | 徐州中矿大贝克福尔科技股份有限公司 | Clinker-free coal ash composite cementing material, preparation method thereof and coal mine filling paste |
| CN115010458A (en) * | 2022-05-16 | 2022-09-06 | 北京安科兴业矿山安全技术研究院有限公司 | Coal mine underground filling material prepared from metal ore overflow tailings and process and application thereof |
| CN114940600A (en) * | 2022-06-16 | 2022-08-26 | 山东理工大学 | Full-solid waste filling material and preparation method thereof |
| CN116354682A (en) * | 2023-03-01 | 2023-06-30 | 中国恩菲工程技术有限公司 | Full-solid waste jet mortar and preparation method thereof |
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