CN1107449A - Decorative colour brick made from tailings - Google Patents

Decorative colour brick made from tailings Download PDF

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Publication number
CN1107449A
CN1107449A CN94101439A CN94101439A CN1107449A CN 1107449 A CN1107449 A CN 1107449A CN 94101439 A CN94101439 A CN 94101439A CN 94101439 A CN94101439 A CN 94101439A CN 1107449 A CN1107449 A CN 1107449A
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CN
China
Prior art keywords
magnesium
mine tailing
tailings
brick
iron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN94101439A
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Chinese (zh)
Inventor
沈兴
沈朴
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN94101439A priority Critical patent/CN1107449A/en
Publication of CN1107449A publication Critical patent/CN1107449A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C04B28/30—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 magnesium cements or similar cements
    • C04B28/32—Magnesium oxychloride cements, e.g. Sorel cement
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0013—Iron group metal compounds
    • C04B2103/0014—Fe
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0015—Noble metal or copper compounds
    • 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
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The tailings of iron and metallic ore, as filler and magnesite cement as cementing agent are used to make colour decorative brick by injection or press moulding. The anionic or cationic modification of magnesite cement is selectively conducted according to components of different tailings. After constant-temp. curing and surficial coating, the mechanical performance of obtained colour brick reaches or is close to that of terrazzo of silicate cement and enamelled brick.

Description

Decorative colour brick made from tailings
The invention belongs to material of construction and solid waste utilizes the field.
The bulk deposition of mine tailing causes the very big harm of society, how to fully utilize mine tailing, brings benefit to the mankind, and is still global problem up to now.Existing tailing-bricks technology, except goods also exist some problems on performance, the economic benefit of its technology own is very little, propose in the CN 1051543A patent documentation with material of construction such as gold concentrator tailings system standard square, hollow brick, paving brick and building blocks, be a kind of non-system tailing-bricks method that adds cement, non-burning, but will be in autoclave maintenance nearly ten hours, facility investment is big, the energy consumption height, and products made thereby all is thick class building materials.
At present, often adopt river sand, extra large sand, rubble, stone flour, coal gangue, slag and sawdust, vermiculite, pearlstone and glass fibre, asbestos and some organic waste materials to make stopping composition in the water-resistant magnesia cement tile product, as United States Patent (USP) 3,482,493; 3,667,978; 3,317,442 and Chinese patent CN 87107780A or the like patent documentation report.Than mine tailing, it forms simple, and granularity is big and can screen.But the proposed invention content but is not suitable for mine tailing in these patent documentations, because as if mine tailing being carried out in advance any processing such as detrimental impurity separation or sintering granulation or washing, screening, oven dry, certainly will improve the technology cost and produce secondary slugs.If mine tailing is dosed as the collocation material, certainly will have been limited the utilization ratio of mine tailing.
The objective of the invention is to, a kind of available all kinds of metal tailings are proposed, particularly make the new prescription and the novel process of colour wall/floor tile as stopping composition with iron tailings and gold deposits tailings, different characteristics at the mine tailing composition, select different additive agent modified dose, its product properties is good, good decorating effect, cheap, economic benefit, obvious social benefit.
The present invention utilizes the high magnesium cement of ultimate compression strength to make jelling agent, utilizes solid waste-all kinds of metal tailings, particularly iron tailings and golden mine tailing to make stopping composition, and does not need through any processing, just can be directly as all dosing material.
In view of changing the characteristics that maybe should not change as the composition of stopping composition mine tailing and the difficulty of form, the present invention has taked the characteristics at the mine tailing composition in the modification of magnesium cement, carry out selecting for use of negatively charged ion, positively charged ion or hybrid ionic properties-correcting agent selectively, to guarantee the mechanical property of azulejo.Generally speaking, iron tailings contains the residue iron of more several forms, select phosphoric acid, monocalcium phosphate or primary magnesium phosphate for use or in hydration process, can discharge anion-modified dose of salt of free phosphorus acid group, be beneficial to the formation of indissoluble tertiary iron phosphate, calcium phosphate etc. in the cured product.The gold mine tailing contains higher fine silica, and selecting calcium chloride, sal epsom for use is properties-correcting agent, is beneficial to the formation of hydrates such as Calucium Silicate powder, Magnesium Silicate q-agent, calcium chloride magnesium.It is that 2%～10% of magnesium oxide weight is advisable that properties-correcting agent adds total amount.This shows that the hydration reaction of mine tailing azulejo is still based on the reaction of activated magnesia and magnesium chloride brine.In its cured product with 518,318 and Mg(OH of needle-like crystal, reticulated structure, microsolubility) 2Xiang Weizhu is attended by the adding of selectivity properties-correcting agent in forming at mine tailing and the generation of salt thing phase that is beneficial to improve azulejo water resisting property of a spot of indissoluble that produces or microsolubility.
Composition of the present invention is 100 parts in (by weight) magnesium oxide, and proportion is magnesium chloride brine 50-60 part of 1.26, pigment 1-30 part, properties-correcting agent industrial phosphoric acid 2-5 part, or double superhosphate chemical fertilizer 5-10 part, or calcium chloride 5-10 part.Mine tailing 100-300 part of the moisture 5-30% of stopping composition is wherein selected phosphoric acid or calcium phosphate chemical fertilizer for use to iron tailings, and gold mine is selected for use calcium chloride.Its processing step for prepare burden in proportion, stirring, moulding, curing, top coat handle, moulding process adopts casting and pressing.
Describe prescription of the present invention and blending process below in detail:
First kind is the prescription and the blending process of casting.
Weight batching ratio for iron tailings notes type azulejo is: 100 parts in magnesium oxide (containing MgO=70-80%), proportion is magnesium chloride brine 50-60 part of 1.26, pigment 1-30 part, industrial phosphoric acid 2-5 part or double superhosphate chemical fertilizer 5-10 part, wet mine tailing (moisture 20-30%) 100-200 part.Its blending process is: earlier with MgCl 26H 2It is that 1.26 the aqueous solution is standby that the O dissolution of crystals becomes proportion.With magnesium chloride brine and magnesium oxide uniform mixing, left standstill 15-30 minute, allow its cementization; Phosphoric acid or phosphate fertilizer and pigment are blended into uniform mixing in the wet mine tailing; Then two kinds of slips are converted together and stirred.In weighing balance or quantitative bale-out viscous paste injected plastic or rubber mold, the shop is even or vibrations are even.The floral designs on azulejo surface depend on mould.Also the slip of two kinds of different colours can be pressed the arbitrary proportion injection molding, the color brick gains freedom.
For golden mine tailing notes type azulejo, only needing change properties-correcting agent phosphoric acid or phosphate fertilizer is calcium chloride, gets final product with same proportioning.
If change the content of MgO in the magnesia powder, then need adjust the magnesium chloride solution amount according to the above ratio.Humidity is controlled to be annotated pattern piece surface and not to produce under the prerequisite of pore, dried partially for well.
Second kind is the prescription and the blending process of compression moulding.
Weight batching ratio for golden mine tailing die mould azulejo is: 100 parts in magnesium oxide (containing MgO=70-80%), proportion are magnesium chloride brine 50-55 part of 1.26, pigment 1-30 part, and industrial calcium chloride 5-10 part is dried mine tailing (moisture 5-8%) 200-300 part.Its process for preparation is :-120 orders that earlier above-mentioned powder all sieved ,-200 orders or-300 orders are then better as if sieving.By the said ratio mixed powder extremely evenly.Adopt the liquid spray method then, under constantly stirring, magnesium chloride solution is sprayed in the powder.It is flat to edge to get or lay powder with the former circle.On pressing machine with the compression moulding of 10-20MPa pressure intensity.
For iron tailings die mould azulejo, only needing with same proportioning change properties-correcting agent calcium chloride is that phosphoric acid or phosphate fertilizer get final product.
The humidity of die mould brick is controlled under the pressure that is adopted, and does not squeeze out under the prerequisite of solution, and is wet partially for well.Moisture content can be by MgCl 26H 2Proportion when O is mixed with the aqueous solution is adjusted.
Compression moulding technology provided by the invention is different from the moulding of refractory brick, ceramic tile and clay brick.The compacting briquet of these bricks can stand up immediately, and the azulejo briquet is easily cracked wet bulk.Taked the water bottom modulus method for this reason.Be that lower floor is the Sheet Steel Form of pressure-bearing, the upper strata bed die of contact material is by both flexible, has the indeformable template of rigidity again under above-mentioned pressure.Can select materials such as rigid plastic sheet, poly (methyl methacrylate) plate, epoxy offset plate, Enplate for use.With the thick four fluorinated ethylene propylene plastic plates of 2mm for well.Compacting back mould base comes along isothermal curing together with the upper strata bed die, throws off template after the curing again, and template is used repeatedly.
Used magnesium oxide among the present invention must be through 800 ± 50 ℃ of calcinings, and granularity is less than 120 orders, and the powder of sealing preservation.This is in order to guarantee that magnesium oxide has enough reactive behavioies, also to make mine tailing that bigger loading level is arranged.Can make with the giobertite calcining that contains MgO=70-80% of medium grade, also can calcine with more low-grade magnesite or particle that contains MgO=50-70%, can also make through thermolysis by magnesium chloride, magnesium hydroxide, brucite or other magnesium salts, even available rhombspar half calcination method makes.But should contain CaO≤5% in all magnesium oxide, and contain potassium, the sodium amount is low.It is high, effective to contain the MgO amount in the magnesia powder, but the price height; But the too low loading level that can influence mine tailing of content., be convenient generally through 800 ± 50 ℃ of light-magnesite powder of burning till with the commercially available magnesite that contains MgO=70-80%.Used magnesium chloride is halogen powder, halogen sheet or the enriched bittern cake of technical grade, requires to contain MgCl 2≮ 46%.
The pigment that the present invention adopts is based on mineral-type.As iron oxide red, cadmium red, molybdenum red; Iron oxide yellow, chrome yellow, zinc yellow; Iron orchid, ultramarine; Green, the chrome green of iron; Iron black, Graphite Powder 99; Zinc white, white lead etc.Iron-based pigment forms insoluble molysite or hydroxide colloid in hydration reaction or azulejo immersion, help improving water tolerance.Pigment dyestuff generally helps improving water tolerance, but has delayed set time, has reduced intensity, so answer strictness to control a small amount of interpolation.
No matter the present invention to being to annotate pattern or die mould base, has taked to place 25-35 ℃ to solidify in case or the curing room air care through 24-48 hour.Utilize the demoulding with elasticity of mould then, after deburring, carry out surface treatment again.This curing case or the curing room device is simple, cost is low carries out the Cryogenic air maintenance, has guaranteed the indeformable and high strength of azulejo.
The present invention has also taked the top coat processing to the azulejo after solidifying, and has improved guarantor's light, guarantor look, weathering resistance and the water tolerance of azulejo greatly, can use E-44 type Resins, epoxy: solvent or diluent=1: 3～5; Or phenolic varnish: solvent or diluent=4～5: 1; Or the coating and the solvent or diluent thereof of other class strong adhesion, weakly alkaline, self-vulcanizing.Also can adopt novel cold ceramic coating and solvent or diluent thereof, it is hard to film, but costs an arm and a leg.Coating can adopt brush and spraying to spray twice for well.
According to the made notes type of the present invention and the mine tailing decorative colour brick of all kinds of die mould, through test, the mechanical property of solidifying after two weeks can both reach: matrix ultimate compression strength ≮ 30MPa, folding strength ≮ 16MPa, surface luster is not moistened water, after 25 circulations of freezing test and water soaking test (soaked 14 hours, second wife's temperature is dried 10 hours for one-period), do not ftracture, not warpage, non-scale, nothing peel off, photochromic constant.Annotate shaped brick water-intake rate＜8%, proportion～2.0g/cm 3; The die mould brick is＜4%, 2.5～4.0g/cm 3Have performances such as weathering resistance, anti-weak acid and weak base corrosion, it is variable with mould also to have a surface detail, and the characteristics that color is various are decorative block of a class novel practical.With Portland cement or building glue bond, be the substitute inexpensive and more attractive in appearance of silicate cement terrazzo and ceramic tile.Because the mine tailing azulejo do not add interior muscle, so lumpiness is suitable little unsuitable big, with 152 * 152 * (5-8) millimeters specifications for well.
The present invention with following embodiment as more detailed description.Raw materials used: magnesite burns till through 800 ± 50 ℃, contains MgO=80%, CaO=2.5%, granularity-120 purpose magnesium oxide.Contain MgCl 2=46.5% industrial hex-ammoniate.The double superhosphate chemical fertilizer, industrial phosphoric acid, industrial calcium chloride, industrial sulphuric acid magnesium.Pigment is industrial iron oxide red, iron oxide yellow, iron oxide black etc.Certain iron ore mine contains T Fe=12.35%, FeO=10.08%, SiO 2=67.87%, Al 2O 3=2.43%, CaO=2.35%, MgO=3.40%, (Na 2O+K 2O)=1.02%, all the other are S, P etc., and-200 orders reach 70%.Certain gold mine tailings contains SiO 2=92.90%, Fe 2O 3=1.10%, CaO=0.49%, MgO=0.56%, all the other are Cu, Pb, Zn, Au, Ag etc. ,-200 orders reach 90%.Preparation is all dried through room temperature with mine tailing.
Example 1 is annotated shaped brick: MgO100g and d=1.26 MgCl 2Solution 55ml mixed and stirred, through cementization 20 minutes.Dry iron tailings 120g and add 25ml water, add 3ml phosphoric acid, add iron oxide red 10g, add iron oxide yellow 3g and mix and stir.Then two kinds of slips are blended into together, stir the back and inject 152 * 152 * 8 millimeters mould of plastics.Put 28 ± 2 ℃ and solidify in the case demoulding deburring after 24 hours.With E-44 type Resins, epoxy: solvent or diluent=weight matched well coating in 1: 4, brushed surface and edge.Dry golden yellow azulejo.Its ultimate compression strength 40MPa, folding strength 20MPa, water-intake rate 6%.
Example 2 die mould azulejos :-120 orders in advance sieve all powders.MgO1kg adds and dries golden mine tailing 2.5kg, adds CaCl 22H 2O 60g adds iron oxide red 200g, electronic stirring in mixer..Under constantly stirring, with d=1.26MgCl 2Solution is sprayed onto in the compound powder through liquid dispenser.With ordinary steel quenching system yin, yang mould, the thick polyfluortetraethylene plate of 2mm makes to go up the bottom template.The shop powder is in former, on double disk friction screw press, with the compression moulding of 15MPa pressure intensity.Adobe is put in 28 ± 2 ℃ of curing casees together with last end template, throws off template after 24 hours.Use phenolic varnish: solvent or diluent=4: 1 coating, sprayed surface and edge twice, room temperature is dried 10 of red azulejos that make 152 * 152 * 5 millimeters specifications.Its ultimate compression strength 50MPa, folding strength 25MPa, water-intake rate 3%.
The mechanical property of azulejo of the present invention reaches or approaches the performance of silicate cement grinding stone and ceramic tile, has high economic benefit and social benefit.

Claims (5)

1, a kind of magnesium cement, metal tailings of containing, it mainly is the decorative colour brick of iron-containing tailing and golden mine tailing, it is characterized in that, composition (by weight) is 100 parts in a magnesium oxide, and proportion is magnesium chloride brine 50-60 part of 1.26, pigment 1-30 part, mine tailing 100-300 part of the moisture 5-30% of stopping composition, properties-correcting agent is selected industrial phosphoric acid 2-5 part for use to iron tailings, or double superhosphate chemical fertilizer 5-10 part, and golden mine tailing is selected for use industrial calcium chloride 5-10 part.
2, decorative colour brick as claimed in claim 1, it is characterized in that, the magnesium oxide that is used to prepare magnesium cement must be through 800 ± 50 ℃ of calcination, granularity is less than 120 orders, and sealing is preserved, the giobertite calcining of the available MgO70-80% of containing, CaO≤5% makes, and also can be made through thermolysis by other magnesium salts.
3, a kind of compound method of decorative colour brick as claimed in claim 1, it is characterized in that, processing step is for preparing burden in proportion, stir, moulding, solidify, top coat is handled, moulding process adopts casting or pressing, casting is that magnesium chloride brine and magnesium oxide are mixed and stirred, left standstill 15-30 minute, allow its cementization, properties-correcting agent and pigment are added in the mine tailing mix and stir in addition, again two kinds of slips are converted the back injection molding that together stirs, pressing is earlier with magnesium oxide, pigment, properties-correcting agent, powders such as mine tailing-120 orders that sieve, mix, adopt liquid spray then, under constantly stirring, magnesium chloride solution is sprayed in the powder, after getting powder with the former circle, with double-deck bed die on pressing machine with the compression moulding of 10-20MPa pressure intensity, the mould base solidifies together with the upper strata bed die.
4, compounding process as claimed in claim 3 is characterized in that, takes in the air cryogenic thermostat to solidify, and waters injection molding or the adobe of the band upper strata bed die that is pressed into all places 25-35 ℃ to solidify in the case, carries out 24-48 hour air care.
5, as claim 3,4 described compounding process, it is characterized in that, take top coat to handle, use E-44 type Resins, epoxy: solvent or diluent=1: 3～5, or phenolic varnish: solvent or diluent=4～5: 1 azulejo after solidifying.
CN94101439A 1994-02-24 1994-02-24 Decorative colour brick made from tailings Pending CN1107449A (en)

Priority Applications (1)

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CN94101439A CN1107449A (en) 1994-02-24 1994-02-24 Decorative colour brick made from tailings

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Application Number Priority Date Filing Date Title
CN94101439A CN1107449A (en) 1994-02-24 1994-02-24 Decorative colour brick made from tailings

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CN1107449A true CN1107449A (en) 1995-08-30

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CN94101439A Pending CN1107449A (en) 1994-02-24 1994-02-24 Decorative colour brick made from tailings

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301930C (en) * 2005-08-16 2007-02-28 西万明 Ecological energy-saving brick sintering from iron mill run gangue
CN102557573A (en) * 2010-12-31 2012-07-11 王浩江 Artificial sandstone and preparation method thereof
CN103449768A (en) * 2013-07-31 2013-12-18 潘逸东 Aerated brick containing waste residues

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301930C (en) * 2005-08-16 2007-02-28 西万明 Ecological energy-saving brick sintering from iron mill run gangue
CN102557573A (en) * 2010-12-31 2012-07-11 王浩江 Artificial sandstone and preparation method thereof
CN103449768A (en) * 2013-07-31 2013-12-18 潘逸东 Aerated brick containing waste residues

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