A kind of mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal and its system
Preparation Method
Technical field
The present invention relates to mine cemented filling, solid wastes recycling utilize and cooperative disposal nickeliferous hazardous waste technical field,
Specifically related to a kind of mine cemented filling material for the nickeliferous hazardous waste of collaborative solidification and preparation method thereof.
Background technology
Current industrial system is actually the process of a production of resources and discharge waste.Mining activity is to environment row
Put the main source of discarded object, its solid waste discharge amount accounts for the 80%~85% of industrial waste discharges amount.Domestic exploitation of mineral resources
Using during the tailings that produces, barren rock, gangue, flyash and metallurgical slag become the maximum industrial solid of discharge capacity and discarded
Thing, accounts for the 85% of national solid waste discharge total amount.Pit mining leaves large-area goaf, the barren rock stacked, waste residue
Field and the tailings dam constructed bring serious place of safety hidden danger and carrying capacity of environment.All types of industries discarded object effectively carries out combination and cooperation
Dispose, be effective measures and the main trend realizing environmental improvement and recycling.
Cemented filling material is typically adopted and is added as aggregate and with cementing agent such as cement with rubble, river sand or Gobi aggregate or tailings
Water mix and blend forms slurry or lotion, is transported to filling area with pipeline pumping or flow by gravity mode.Cemented filling material contains
A certain proportion of cementing agent, has higher intensity and globality, has higher operational security, props up meeting various down-holes
The rate of extraction of ore and the operating efficiency of stope can be improved while support demand.With filling in mine mining technique popularization with
Application, cementing agent for filling is also constantly updating the replacement, is that large industrial solid castoff recycling provides effective way
Footpath.Cement has high energy consumption in itself as building trade cementing agent the most common, its production technology, with serious pollution feature.
In recent years, a large amount of novel gelled materials of appearance, are essentially all to enter on the basis of Portland cement or slag cements
Row improves, even if with slag, the coal ash instead part of cement grog with hyperpyrexia history, but the restriction due to raw material, takes
For clinker quantity low, cementing result is undesirable etc., and aspect restricts its popularization and application.
Industrial solid castoff is divided into general solid waste and hazardous waste.《Prevention and control of environmental pollution by solid wastes method》The
Article 74, Section 4 regulation, list in National Hazard waste register or the hazardous waste judging standard according to national regulation and
The waste with hazard property of discrimination method identification, belongs to hazardous waste.Accordingly, though certain class waste excludes《National Hazard gives up
Name is recorded》, but if the hazardous waste judging standard according to national regulation and discrimination method assert that it has hazard property, also belong to danger
Dangerous waste.Hazardous waste has the harm such as combustibility, corrosivity, acute toxicity, Leaching, reactivity, infectiousness, radioactivity
Characteristic.In recent years, the impact to environment and health for the hazardous waste is increasingly subject to the concern of the public and law.Having in hazardous waste
Evil material can not only cause directly to endanger, and also can migrate in the natural environments such as soil, water body, air, be detained, convert, dirty
The ecological environments for the survival of mankind such as dye soil, water body, air, thus eventually affect ecology and health.In hazardous waste
During " 3R " (resource, minimizing, innoxious), minimizing and innoxious is realized by incineration treatment technology, reclaiming has valency
Composition realizes resource.No matter adopted which kind of technology, all can produce needs the remnants of final disposal during dangerous waste disposal
Thing, security landfill in prior art is final disposal technology, is also the higher technology of environmental risk, both at home and abroad to security landfill
The addressing of field, antiseepage etc. require very high.Because safety fills up the safe disposal mode of simply hazardous waste, do not have " harmless
The effect of change ", so percolate, landfill gas, still can cause latency environment to pollute, therefore, in hazardous waste security landfill
Before, mostly need to carry out hazardous waste curing/stabilizing process.Curing/stabilizing technology is by adding curing agent or steady
Determine agent, reduce the toxicity of hazardous waste and transportable property, the curing/stabilizing technology of current comparative maturity has:Cement solidification method,
Lime solidification method, plasticity solidification method, melting and solidification method, from cementation solidifying method and chemical stabilization technology etc..Solid in prior art
Change/stabilization technology is faced with high cost, increase-volume fills the big problem of floor space than big, Subsequent secure.
Content of the invention
The present invention relates to a kind of mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal and preparation method thereof,
It is to solve problems with of the prior art:
1. cemented filling mining high cost, cement consumption be big, early strength is low;
2. large industrial solid castoff, such as tailings, slag, slag, storing up in a large number of industry by-product gypsum cause resource
Waste and environmental pollution;
3. during hazardous waste safe disposal, high cost, increase-volume are bigger than big, security landfill field floor space.
Present invention achieves cooperative disposal solid waste substitutes cement preparation mine cemented filling material;Achieve collaborative
The nickeliferous hazardous waste of safe disposal is so as to reach drinking water standard by the toxicity of lixivium that toxicity leaching method obtains;Realizing will
Firming body after " innoxious " curing process, casting resin is filled with underground mining dead zone, saves the large area that security landfill place needs
Soil.
Realizing the technical scheme that above-mentioned purpose of the present invention adopted is:
A kind of mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal, including cementing agent, gather materials, water reducer
With nickeliferous hazardous waste it is characterised in that:By weight percentage, described cementing agent includes slag 30%~90%, slag 0%
~50%, industry by-product gypsum 5%~20%.
Described cementing agent be also possible that cement, mine tailing, granulation electric furnace phosphoric slag, granulation ferrochrome slag, flyash, carbide slag,
Red mud, alkaline residue, one or more of gangue.
Described gather materials including mountain sand, river sand, one or more composition of tailings or barren rock.
Described water reducer be lignin sulfonate water reducer, naphthalene series high-efficiency water-reducing agent, melamine superplasticizer,
Amino-sulfonic Acid-based Water-reducer, fatty acid series high efficiency water reducing agent, one or more of polycarboxylate high-efficiency water-reducing agent.
Described nickeliferous hazardous waste be by《Solid waste Leaching method horizontal vibration method》(HJ557-2009) specify
Leaching program leaching experiment is carried out to solid waste, in leachate, nickel concentration is more than GB5083.3-2007《Hazardous waste differentiates
Standard-leaching characteristic identification》The hazardous solid waste of threshold value 5mg/L of defined.
The granulated blast furnace slag that the slag water that described slag produces for metallurgy high furnace ironmaking processes is formed after rapidly cooling down,
It is also referred to as grain slag or Water Quenching Slag, main chemical scope is:CaO38%~49%, SiO226%~42%, Al2O36%
~17%, MgO1%~13%, MnO0.1%~2%, FeO0.07%~2.5%, S0.2%~1.5%.Other indexs meet
The requirement of GB/T18046-2008.
Described steel-making slag powder is the slag producing in steelmaking process, wherein tricalcium silicate content C3S 5%~30%, silicic acid
Two calcium content C2S 5%~30%, RO phase content 10%~38%, ferric oxide content 2%~8%, calcium hydroxide content
0.5%~5%, iron hydroxide content 0.5%~5%, free calcium oxide content 0.01%~3%, calcium carbonate content 0.01%
~10%, carbonic acid content of magnesium is 0.01%~8%, and carbonic acid iron content is 0.01%~3%, other 0.01%~3%.Other refer to
Mark meets the requirement of GB/T 20491-2006.
Described industry by-product gypsum refer in industrial production by chemical reaction generate (predominantly anhydrous and two with calcium sulfate
H 2 O calcium sulphate) for main component industry byproduct, include desulfurated plaster, ardealite, fluorgypsum, lemon gypsum, give up Tao Moshi
One or more of cream.
The mechanism of action of this cementing agent is as follows:
Casting resin can obtain good intensity so as in cementing agent aquation to produce enough C-S-H gel be core
Problem.And to (SiO in the maximum C-S-H gel of casting resin intensity contribution2+Al2O3)/(CaO+MgO) mol ratio 0.6~
Within the scope of 0.8.Existing enough results of study show that this ratio in C-S-H gel in the range of this is higher, and it is right
The intensity contribution of casting resin is bigger.C-S-H gel is the chain columnar structure silicate being formed by connecting by silicon-oxy tetrahedron, and water quenching grain
Change (SiO in blast-furnace cinder2+Al2O3)/(CaO+MgO) mol ratio more than 0.9.
(SiO in slag2+Al2O3)/(CaO+MgO+FeO) ratio is very low, and generally below 0.15.If therefore slag is worn into
Micro mist, slag micro powder is the gel hardening of casting resin and gain in strength provides the tetrahedral ability of silicon (aluminium) oxygen extremely weak.In C-S-H
In gel, not only a large amount of silicon-oxy tetrahedrons can be replaced by aluminum-oxygen tetrahedron and a certain amount of iron oxygen tetrahedron, and therein
Calcium ion can be replaced by divalent ions such as substantial amounts of magnesium ion, ferrous ions.Therefore, thin if steel-making slag powder can be worn into micron order
Powder, so as to hydration reaction can comparatively fast occur, just can provide substantial amounts of divalent metal for gelling system.
In granulated blast-furnace slag, the content of aluminum oxide is typically higher, and with alumina four sides in the vitreum of blast-furnace cinder
Body form and silicon-oxy tetrahedron link.When the higher ph solution that blast-furnace cinder and slag are formed contacts, aluminum-oxygen tetrahedron
Tend to depolymerization from the link of silicon-oxy tetrahedron and enter solution.In the presence of having more gypsum in system, calcium can quickly occur
The crystallization reaction of aluminite.
4H3AlO4 2-+6Ca2++6CaSO4·2H2O+4OH-+44H2O→2
(3CaO·Al2O3·3CaSO4·32H2O)
Entringite is the very low double salt of a solubility.C.B.Satish etc. in Chemical Geology, (148)
1998, in the 1-19 page, the entringite solubility product constant of report is 10-111.6.It constantly crystallizes and leads to Al in solution3+Ion is dense
The reduction of degree, makes the balance of above-mentioned reaction equation move right, and reaction is constantly carried out.Al3+A large amount of dissolutions of ion make granulated blast-furnace
Aluminum-oxygen tetrahedron in slag micropowder and silicon-oxy tetrahedron link disconnection, and so that remaining silicon-oxy tetrahedron activity is significantly carried
Height, thus constantly producing the tetrahedral depolymerization of silicon (aluminium) oxygen, creates condition to the generation of a large amount of C-S-H gels.
The generation of a large amount of C-S-H gels not only needs silicon (aluminium) the oxygen four sides of activity in a large number, and need substantial amounts of calcium,
The bivalent cations such as magnesium, iron.And the aquation of slag can effectively provide these divalent metals.Therefore wear into micron-sized
Superfine steel slag micropowder and blast furnace slag micro mist, industry by-product gypsum micro mist synergy, can be made into the mine substituting cement
Cementing agent for filling.
A kind of preparation method of the mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal it is characterised in that:
By activated process after cementing agent with gather materials, nickeliferous hazardous waste, water reducer, add water and mix, comprise the following steps that:
(1) the needed raw material slag of moisture content 0.01%~1%, slag, industry by-product gypsum are pressed butt weight percent
Than with 30%~90%, 0%~50%, 5%~20% independent or combined grinding to specific surface area 200~600m2/ Kg, with water
Mud, mine tailing, granulation electric furnace phosphoric slag, granulation ferrochrome slag, flyash, carbide slag, red mud, alkaline residue, one or more warp of gangue
Mix after activation process and cementing agent is obtained;
(2) nickeliferous hazardous waste is dried to moisture content 0.01%~1% grinding to specific surface area 100~1000m2/ Kg,
By cementing agent/weight of gathering materials than for 1/4~1/8, the weight of nickeliferous hazardous waste/(cementing agent+gather materials) is than for 1/100~1/
10, add water reducer 0%~1%, pulp quality fraction is 65%~82%, stirs and just can get qualified mine glue
Knot casting resin.
Described activation process includes grinding, calcining, one or more processing mode of alkali-activated carbonatite.
After described casting resin solidification, the leaching concentration of nickel is≤20 μ g/L less than drinking water standard.
Compared with prior art, tool beneficial effect and advantage are the present invention:
1. the raw material more than 90% of mine cemented filling material derives from industrial solid castoff.
2. mine cemented filling material is while processing industrial solid castoff, and the nickeliferous hazardous waste of cooperative disposal is real
The existing treatment of wastes with processes of wastes against one another.
3. the intensity of the mine cemented filling material of the nickeliferous hazardous waste of cooperative disposal meets the requirement of the method for mining by the way of filling, with
When nickel Steep cencentration below drinking water standard, fully achieve " innoxious ", and save the large area needed for security landfill
Soil.
4. the preparation method of the mine cemented filling material of the nickeliferous hazardous waste of cooperative disposal is very simple to operation, energy consumption
Low, equipment used is very common, thus low cost, do not have new solid waste to produce, environmental pollution very little, very ring
Protect.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
A kind of mine gelling agent, is prepared from by the raw material of following percentage by weight:
Slag 54%
Slag 35%
Desulfurated plaster 11%
A kind of preparation method of the mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal it is characterised in that:
By activated process after cementing agent with gather materials, nickeliferous hazardous waste, water reducer, add water and mix, comprise the following steps that:
(1) respectively by needed raw material slag, slag, desulfurated plaster is dried to moisture content 0.01%~1%, then by ore deposit
Slag, slag, desulfurated plaster press butt percentage by weight respectively with 54%, 35%, 11% separate grinding to specific surface area 450m2/
Kg、480m2/Kg、360m2/ Kg mixes in batch mixer and cementing agent is obtained;
(2) nickeliferous hazardous waste is dried to moisture content 0.01%~1% grinding to specific surface area 150m2/ Kg, by cementing
For 1/4, the weight of nickeliferous hazardous waste/(cementing agent+gather materials) ratio for 1/20, adds sulfomethylated lignin acids to agent/weight of gathering materials ratio
Water reducer 0.4%, pulp quality fraction is 81.94%, stirs and just can get qualified mine cemented filling material.
It is 5.7mg/L that the nickel toxicity of nickeliferous hazardous waste garbage flying ash leaches result.
Gather materials from Pb-Zn deposits classified tailingses.
It is unlimited that prepared by experiment one, embodiment 1 carries out single shaft for the collaborative cemented filling material solidifying nickeliferous hazardous waste
Survey compression strength experiment and nickel toxicity leaching experiment.
1. experimental technique
1) experimental group:Casting resin described in embodiment 1 is injected in the standard test mode of 70.7 × 70.7 × 70.7mm, with vibration
Platform shakes 30s;
2) control group:With 42.5 class g cements as cementing agent, other steps are identical with test group;
3) experimental group and control group is quiet stops form removal after maintenance 24h, is respectively put into standard curing box and carries out maintenance, until age
Node carries out the test of single shaft unconfined compressive strength and nickel toxicity leaching test respectively.
2nd, experimental result
1) single shaft unconfined compressive strength test result is as shown in the table:
2) the nickel Steep cencentration result of test group full solid waste adhesive bond is as follows:
ND refers to that nickel leaching concentration is less than detection limit
Embodiment 2
A kind of mine gelling agent, is prepared from by the raw material of following percentage by weight:
A kind of preparation method of the mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal it is characterised in that:
By activated process after cementing agent with gather materials, nickeliferous hazardous waste, water reducer, add water and mix, comprise the following steps that:
(1) respectively needed raw material slag, slag, ardealite are dried to moisture content 0.01%~1%, then by slag,
Slag, ardealite press butt percentage by weight respectively with 45%, 20%, 13% separate grinding to specific surface area 400m2/Kg、
460m2/Kg、360m2/ Kg, is respectively 15%, 7% to moisture content 0.01%~1% by butt percentage by weight with being respectively dried
Grinding is to 360m2/Kg、300m2The granulation ferrochrome slag of/Kg, flyash mix in batch mixer and cementing agent are obtained;
(2) nickeliferous hazardous waste is dried to moisture content 0.01%~1% grinding to specific surface area 200m2/ Kg, by cementing
Than for 1/5, than for 1/15, pulp quality fraction is agent/weight of gathering materials for the weight of nickeliferous hazardous waste/(cementing agent+gather materials)
70%, stir and just can get qualified mine cemented filling material.
It is 6.1mg/L that the nickel toxicity of nickeliferous hazardous waste wastewater treatment mud leaches result.
Gather materials from Pb-Zn deposits crude tailings and river sand, the mass ratio of Pb-Zn deposits crude tailings and river sand is 4/1.
It is unlimited that prepared by experiment two, embodiment 2 carries out single shaft for the collaborative cemented filling material solidifying nickeliferous hazardous waste
Survey compression strength experiment and nickel toxicity leaching experiment.
1. experimental technique
1) experimental group:Casting resin described in embodiment 2 is injected in the standard test mode of 70.7 × 70.7 × 70.7mm, with vibration
Platform shakes 30s;
2) control group:With 32.5 class g cements as cementing agent, other steps are identical with test group;
3) experimental group and control group is quiet stops form removal after maintenance 24h, puts into maintenance in 40 DEG C of steam boxes, until age node divides
Do not carry out the test of single shaft unconfined compressive strength and nickel toxicity leaching test.
2nd, experimental result
1) single shaft unconfined compressive strength test result is as shown in the table:
2) the nickel Steep cencentration result of test group full solid waste adhesive bond is as follows:
ND refers to that nickel leaching concentration is less than detection limit
Embodiment 3
A kind of mine gelling agent, is prepared from by the raw material of following percentage by weight:
A kind of preparation method of the mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal it is characterised in that:
By activated process after cementing agent with gather materials, nickeliferous hazardous waste, water reducer, add water and mix, comprise the following steps that:
(1) respectively needed raw material slag, slag, desulfurated plaster, fluorgypsum are dried to moisture content 0.01%~1%, so
Afterwards slag, slag, desulfurated plaster, fluorgypsum are pressed butt percentage by weight respectively with 42%, 20%, 8%, 5% separate grinding
To specific surface area 480m2/Kg、510m2/Kg、330m2/Kg、310m2/ Kg, presses butt with drying to moisture content 0.01%~1%
Percentage by weight be respectively 15%, 10% individually levigate to 440m2/Kg、370m2The granulation electric furnace phosphoric slag of/Kg, carbide slag are mixed
Mix in material machine and cementing agent is obtained;
(2) nickeliferous hazardous waste is dried to moisture content 0.01%~1% grinding to specific surface area 200m2/ Kg, by cementing
Than for 1/7, than for 1/25, pulp quality fraction is agent/weight of gathering materials for the weight of nickeliferous hazardous waste/(cementing agent+gather materials)
72%, stir and just can get qualified mine cemented filling material.
It is 7.1mg/L that the nickel toxicity of the waste residue producing in nickeliferous hazardous waste cadmium nickel battery production process leaches result.
Tailings selects iron ore crude tailings.
It is unlimited that prepared by experiment three, embodiment 3 carries out single shaft for the collaborative cemented filling material solidifying nickeliferous hazardous waste
Survey compression strength experiment and nickel toxicity leaching experiment.
1. experimental technique
1) experimental group:Casting resin described in embodiment 3 is injected in the standard test mode of 70.7 × 70.7 × 70.7mm, with vibration
Platform shakes 30s;
2) control group:With 32.5 class g cements as cementing agent, other steps are identical with test group;
3) experimental group and control group is quiet stops form removal after maintenance 24h, is respectively put into maintenance in 40 DEG C of steam boxes, until age
Point carries out the test of single shaft unconfined compressive strength and nickel toxicity leaching test respectively.
2nd, experimental result
1) single shaft unconfined compressive strength test result is as shown in the table:
2) the nickel Steep cencentration result of test group full solid waste adhesive bond is as follows:
ND refers to that nickel leaching concentration is less than detection limit
Embodiment 4
A kind of mine gelling agent, is prepared from by the raw material of following percentage by weight:
A kind of preparation method of the mine cemented filling material for the nickeliferous hazardous waste of cooperative disposal it is characterised in that:
By activated process after cementing agent with gather materials, nickeliferous hazardous waste, water reducer, add water and mix, comprise the following steps that:
(1) respectively needed raw material slag, slag, desulfurated plaster are dried to moisture content 0.01%~1%, then by ore deposit
Slag, slag, desulfurated plaster press butt percentage by weight respectively with 55%, 22%, 8% separate grinding to specific surface area 420m2/
Kg、450m2/Kg、380m2/ Kg, presses butt percentage by weight respectively 5%, 2% list with drying to moisture content 0.01%~1%
Solely levigate to 420m2/Kg、250m2The cement of/Kg, iron tailings and dry to moisture content 0.01%~1% by butt weight percent
Cementing agent is obtained than mixing in batch mixer through the red mud that alkali-activated carbonatite is processed for 8%;
(2) nickeliferous hazardous waste is dried to moisture content 0.01%~1% grinding to specific surface area 300m2/ Kg, by cementing
Than for 1/6, than for 1/20, pulp quality fraction is agent/weight of gathering materials for the weight of nickeliferous hazardous waste/(cementing agent+gather materials)
75%, stir and just can get qualified mine cemented filling material.
The nickel toxicity that nickeliferous hazardous waste discards nickel-containing catalyst leaches result for 6.6mg/L.
Tailings selects iron ore crude tailings.
It is unlimited that prepared by experiment four, embodiment 4 carries out single shaft for the collaborative cemented filling material solidifying nickeliferous hazardous waste
Survey compression strength experiment and nickel toxicity leaching experiment.
1. experimental technique
1) experimental group:Casting resin described in embodiment 4 is injected in the standard test mode of 70.7 × 70.7 × 70.7mm, with vibration
Platform shakes 30s;
2) control group:With 32.5 class g cements as cementing agent, other steps are identical with test group;
3) experimental group and control group is quiet stops form removal after maintenance 24h, is respectively put into maintenance in 40 DEG C of steam boxes, until age
Point carries out the test of single shaft unconfined compressive strength and nickel toxicity leaching test respectively.
2nd, experimental result
1) single shaft unconfined compressive strength test result is as shown in the table:
2) the nickel Steep cencentration result of test group full solid waste adhesive bond is as follows:
ND refers to that nickel leaching concentration is less than detection limit
Can be seen that the present invention from test one to the intensity test result of test four and nickel leaching concentration result provides
Cementing agent for filling in mine have a clear superiority with solidified cement body intensity aspect;The nickel leaching concentration of firming body different larval instar is equal
Below drinking water standard.In a word, this is used for the preparation process is simple of the useless cemented filling material of the nickeliferous dangerous danger of cooperative disposal, by force
Degree is high, solidifies nickel excellent effect.