CN101100365A - Method for producing low-temperature ceramic stone - Google Patents

Method for producing low-temperature ceramic stone Download PDF

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Publication number
CN101100365A
CN101100365A CNA2007101375847A CN200710137584A CN101100365A CN 101100365 A CN101100365 A CN 101100365A CN A2007101375847 A CNA2007101375847 A CN A2007101375847A CN 200710137584 A CN200710137584 A CN 200710137584A CN 101100365 A CN101100365 A CN 101100365A
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waste residue
slag
agent
parts
less
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张召述
夏举佩
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CNA2007101375847A priority Critical patent/CN101100365A/en
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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

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Abstract

This invention relates to a method for production of artificial low temperature ceramic stone by using slag-muck as raw material. The raw material components, with the weight ratio, are: slag after treatment: raw material slag: modifying agent: accelerator: surface-active-agent=100:(30-60):(10-50):(0.5-7):(0.03-2.0). The production procedures of this invention are: raw material treatment, preparing raw materials, formation, curing, drying, finishing, so obtained is the inventive low temperature ceramic stone containing mainly silica-alumina as base material. This invention products thus produced have advantages of: no use of cement, no use of gypsum or plastic adhering agent, no need of high temperature or high pressure during production, producing no toxic gas, low cost, high reutilization of wastes, saving natural resources and environmental-protection.

Description

A kind of production method of low-temperature ceramic stone
One, technical field: the present invention relates to a kind of low-temperature ceramic stone production method made from waste residue, belong to building material technical field.
Two, background technology: the annual production of large solid waste such as the waste residue of China such as flyash, coal gangue, metallurgical slag, phosphorus slag has reached 900,000,000 tons, accumulative total over the years is stored up nearly 7,000,000,000 tons, utilization ratio less than 50%, large utilization mainly at silicate cement, concrete, wall body brick, build the road, aspect the backfill.
Residual residue behind plant residuum such as straw, bagasse, tobacco rod, shell, bark, branch, weeds and the economic plants processing extracting effective components is that occurring in nature is the abundantest and can the regenerated biomass resource, China only annual production of straw just reaches more than 700,000,000 ton, most of being committed to the flames, both polluted air was wasted resource again.In the known plant residuum resource scheme, more representational technology has following several: return crop stocks to the field, ammoniated forage, humic fertilizer material, fuel, wood-based plate (fiberboard, shaving board, laminate), activated carbon, papermaking etc., wherein wood utilization is the main path of plant refuse, and the various imitation woods of domestic production at present mainly contain three types: the one, and be the artificial board of binding agent with thermosetting polymer such as urea-formaldehyde resin, resol; The 2nd, be the shaving board of binding agent with cement, gypsum, magnesite; The 3rd, be the Wood-plastic material of representative with thermoplastic polymer such as polyethylene, polyvinyl chloride.Cost of development is low, performance good, new variety imitation wood nontoxic, environmental protection still is the developing direction of plant refuse resource utilization from now on.
Based on natural and imitation wood exist such as moisture expansion and drying shrinkage, poor mechanical property, not water-fast, not fire-retardant, be afraid of to damage by worms, perishable problem such as rotten, Chinese scholars is mainly studied from the Wooden modifying aspect, and has obtained progress aspect the woodceramics of property, ceramic timber, metallization timber, Calucium Silicate powder chain timbers material, the polymkeric substance timber having.
Woodceramicsization is the important channel of Wooden modifying, but mainly be to carry out osmotic treated with ethyl silicate and soluble metal salt pair base material in the past, these methods can not form successive ceramic body structure, just must be and will obtain the ceramic body structure through high-temperature calcination, but what finally obtain is the woodceramics that does not have wood feature fully.That is to say that known technology does not also have really to realize the pottery modification of timber.
The main component of waste residue generally is made up of silicon-dioxide, aluminum oxide, calcium oxide, ferric oxide, magnesium oxide, sodium oxide, handle by appropriate means, its original silicate sturcture energy depolymerization, and can be that polymerization once again forms new silicate network under the ambient condition with water, performance with stupalith, but, therefore be called low-temp ceramics because the process that ceramic body forms does not have the high temperature sintering of traditional ceramics.Finish near under the normal temperature condition because of the formation of its structure, can adopt several different methods to carry out modification, avoiding the high temperature may be incompatible with chemistry the thermal mismatching that additive constitutes; Low-temp ceramics gelling material and the plant refuse made with industrial residue carry out compounded low temperature ceramic timber, but have pottery concurrently nontoxic, fire-retardant, stable, durable, water-fast, corrosion-resistant, wear-resisting, anti-damage by worms and the lightweight of timber, pliable and tough, ventilative, can process and decorate properties, be expected aspect acquisition widespread uses such as, building structure heat insulation at building decoration, construction wall, building heat preservation with its advantage performance.
Three, summary of the invention:
The purpose of this invention is to provide a kind of method, utilize the physicochemical characteristic of industrial residue, at first be prepared into the low-temp ceramics gelling material that the energy aquation is solidified with waste residue and plant refuse system low temperature ceramic timber; Carry out the compound low temperature ceramic timber that is prepared into this gelling material and plant refuse with good physical and mechanical property, use to substitute day by day rare natural timber and deleterious imitation wood, thereby the realization that continues the strategic objective that do not wane forever for China's ecotope benign cycle and the utilization of resources is made contributions.
Technology contents of the present invention
1, raw material and prescription
1) main raw material
First kind main raw material is that waste residue comprises cullet, glass fibre waste residue, flyash, phosphorus slag, metallurgical slag, municipal refuse incineration slag, they have passed through high-temperature calcination or fusion in production process, these industrial residues can use in independent or two or more arbitrary proportion collocation;
The second class main raw material is a plant refuse, comprises straw, wheat straw, corn stalk, bagasse, tobacco rod, shell, sawdust, bark, branch, weeds, and they both can use separately, but also two or more mix and match uses.
2) additive: comprise properties-correcting agent, promotor, tensio-active agent three classes.
Properties-correcting agent is the aqueous solution of water glass, and density is 1.30-1.52g/ml, and modulus is 3.7-2.0;
Promotor is a kind of in calcium silicofluoride, Sodium Silicofluoride, potassium silicofluoride, the caustic soda or two or more uses by the arbitrary proportion collocation arbitrarily;
Tensio-active agent is a kind of in trolamine, calcium lignin sulphonate, sodium lignosulfonate, sulfonated melamine compound resin, the naphthalenesulfonate or two or more uses by the arbitrary proportion collocation arbitrarily;
3) prescription (by weight)
Waste residue: plant refuse: properties-correcting agent: promotor: tensio-active agent=100: 30-600: 10-50: 0.5-7: 0.03-2.0;
4) Pei Fang the scope of application
(1) waste residue, plant refuse and properties-correcting agent quality all comprise the moisture content that nature or treating processes are brought into;
(2) in the prescription plant refuse replace to waste residue (cullet, glass fibre waste residue, flyash, phosphorus slag, metallurgical slag, municipal refuse incineration slag), what prepare is the low-temp ceramics matrix material, does not have timber but has the stone material feature.
2, the present invention finishes by following production stage:
1) raw material is handled: waste residue comprises in cullet, glass fibre waste residue, flyash, phosphorus slag, metallurgical slag, the municipal refuse incineration slag if water ratio greater than 5%, needs to add the aqueous 30-50 weight of waste residue % unslaked lime, and mixes ageing 1-12 hour; If water ratio is less than or equal to 5 weight % and can directly uses; Waste residue and promotor, tensio-active agent combined grinding are made granularity and are accounted for the 85%-100% mixed powder less than 0.08mm;
Plant refuse needs fragmentation to be processed into length 0.5-150mm, width 0.5-10mm, thickness 0.1-5mm shape, both can directly use, also the available processes agent is soaked or the digestion processing, treatment agent is one or more the aqueous solution in lime, water glass, yellow soda ash, borax, sodium phosphate, Tai-Ace S 150, the potassium aluminium sulfate, the consumption of treatment agent is the 0.5-15 weight % of plant refuse, the treatment agent concentration of aqueous solution is 0.01-5.0 weight %, the natural immersion time is 1-15 days, the digestion time is 2-6 hour, and digestion temperature is 60-95 ℃;
2) compound preparation: mixed powder and properties-correcting agent, the plant refuse of handling are mixed into compound;
3) moulding: when moisture content in the compound during, compression moulding less than 20 weight %, forming pressure 0.1-3.0MPa, hot pressing temperature is 60-198 ℃, the dwell time is 5-55 minute; When moisture content in the compound during more than or equal to 20 weight %, with vibrating, extrude and casting.
4) maintenance: it is in 65-175 ℃ the wet-hot steam environment maintenance 6-36 hour that moulded products is placed after 12-36 hour in temperature naturally again;
5) drying: after the goods maintenance is finished, adopt air-dry, the sun to shine or baker carries out drying and dehydrating, when the quality water ratio becomes work in-process during less than 5 weight %.
6) decorate processing: work in-process are after super-dry, need polish flat, paint, one of coating, woodgrained paper pastes and decorates or use by unsaturated polyester resin, mineral filler, solidifying agent, setting accelerator one or more to mix ornament layers and carry out coating processing, after treating surface solidification, polish, become product.
Present technique compared with prior art has following advantage:
1, compare with known imitation wood, the present invention is without thermoplastics, thermosetting resin binding agent, avoided high molecular polymer degraded, additive discharges, residue volatilization (as formaldehyde) causes Toxic pollution problem fully; Fire prevention, waterproof, fire-retardant, the smoke elimination problem of timber have fundamentally been solved simultaneously.
2, compare with traditional shaving board, it is gelling material that the present invention adopts waste residue, final what form is the strong structure with ceramic performance, has avoided cement, gypsum as the insurmountable moisture expansion and drying shrinkage of shaving board gelling material, intensity is low, the life-span is short problem.
3, main raw material of the present invention is waste residue and plant refuse, and abundant raw material is with low cost; Goods have the stability of pottery, fire-retardant, nontoxic, hardness is high, wear resistance is good feature, have lightweight, insulation, shock-resistant and machinable performance of timber simultaneously.
Four, description of drawings: Fig. 1 is technical process of the present invention.
Five, embodiment
Embodiment 1:
Getting the quality water ratio and be 100 parts, 0.8 part wooden calcium sulfonate of phosphorus slag of 1.2%, 0.03 part of trolamine, 2 parts of Sodium Silicofluoride blend grindings becomes granularity to account for 95% powder less than 0.08mm; Being broken into length earlier for 550 parts in the sawdust/straw/weeds=plant refuse of 1/1.25/0.5 ratio cooperation is 100-150mm, then with treatment agent aqueous solution digestion, treatment agent is the mixed aqueous solution for water glass, lime, yellow soda ash, three kinds mass ratio is 1/2/1.5, the consumption of treatment agent is 10 weight % of plant refuse, concentration is 4.5 weight %, digestion 4 hours, digestion temperature is 75 ℃, getting the good powder of grinding is 1.36g/ml with plant refuse and the density handled, modulus is 18 parts of 3.5 water glass, and stirring became compound in 7 minutes; Inject the mould moulding of vibrating, placement demoulding after 12 hours naturally was placed in 80 ℃ the sweating room maintenance 8 hours, and drying and dehydrating when water ratio becomes work in-process less than 5% the time, is tested its density 0.92g/cm 3, ultimate compression strength 15Mpa, folding strength 7Mpa.Use the alkyd paint cover behind the surface grinding, have wood effect.
Embodiment 2:
Get 60 parts in flyash, 20 parts of cullet, 20 parts in glass fibre waste residue, the quality water ratio of three kinds of waste residues is followed successively by 8.6%, 6.8%, 4.6%, amount to that the quality water ratio is 7.44% in the waste residue, add 3.6 parts of unslaked limes in waste residue, the mixing ageing adds 0.06 part of trolamine after 6 hours, 7 parts of potassium silicofluoride blend grindings become granularity to account for 85% powder less than 0.08mm; The plant refuse that cooperates in corn stalk/wheat straw/eucalyptus branches and leaves=1/0.5/0.5 ratio is broken into length earlier less than 150mm, width is less than 10mm, thickness is less than fibrous 600 parts of 5mm, with mass concentration is 3% lime aqueous solution mixing digestion, lime consumption is 8 weight % of plant refuse, digestion 3 hours, digestion temperature is 75-95 ℃, get the good powder of grinding, the plant refuse of handling, density is 50 parts of 3 water glass for the 1.50g/ml modulus, stir casting after 10 minutes, naturally place the demoulding in 24 hours, with 95 ℃ atmospheric steam curings 8 hours, dry to water ratio less than becoming work in-process, the density 0.85g/cm of this test material at 5% o'clock 3, ultimate compression strength 8Mpa, folding strength 6.2Mpa is that binding agent, woodgrained paper are veneer with white glue with vinyl behind the surface grinding, has wood effect.
Embodiment 3:
Get 40 parts of phosphorus slags, 30 parts of copper ashes, 30 parts in slag, the quality water ratio of three kinds of waste residues is followed successively by 9.6%, 4.5%, 6.6%, amount to that the quality water ratio is 7.17% in the waste residue, in waste residue, add 2.5 parts of unslaked limes, mix ageing and add 3.0 parts of 0.1 part of trolamine, calcium silicofluorides after 10 hours, 4.0 parts in caustic soda, blend grinding become fineness to become granularity to account for 92% powder less than 0.08mm; 200 parts of the plant refuses that cooperates in peanut hull meal/husk/rice bran=1/0.4/0.6 ratio, being broken into overall dimension earlier is 1-10mm, be 4.2% treatment agent aqueous solution digestion then with mass concentration, digestion 6 hours, digestion temperature is 70-80 ℃, borax in the treatment agent, sodium phosphate, Tai-Ace S 150, the mass ratio of potassium aluminium sulfate is 1/3.5/1.6/5, its consumption is 2 weight % of plant refuse, get the good powder of grinding, the plant refuse of handling, density is 1.50g/ml, modulus is 30 parts of 2 water glass, stirring became compound in 5 minutes, and extrusion moulding was placed after 30 hours in 65 ℃ hygrothermal environment maintenance 36 hours naturally, being dried to water ratio became work in-process less than 5% o'clock, tested the density 1.25g/cm of this material 3, ultimate compression strength 12Mpa, folding strength 6.2Mpa; Use behind the surface rubbing that (mass ratio is: the decorating glue of 1/1/0.1/0.05) forming applies 1mm, polishes after the surface solidification, and the surface has stone materialization decorative effect by unsaturated polyester resin, aluminium hydroxide, methylethyl ketone peroxide, cobalt naphthenate.
Embodiment 4:
Get 50 parts of nickel slags, 30 parts in slag, 20 parts in flyash, the quality water ratio of three kinds of waste residues is followed successively by 5.6%, 4.5%, 12.6%, amount to that the quality water ratio is 6.67% in the waste residue, add 2.7 parts of unslaked limes in waste residue, mix ageing and add 1.0 parts of wooden calcium sulfonates after 8 hours, 4 parts of blend grindings of potassium silicofluoride become granularity to account for 99% powder less than 0.08mm; 150 parts of the plant refuses that cooperates in tobacco rod/straw powder=1/2 ratio, broken earlier grow up fibrous less than 0.5mm's less than 150mm, width less than 5mm, thickness; Getting the good powder of grinding, the plant refuse of handling, density is 1.35g/ml, modulus is that 2.5 water glass mixes for 20 parts and stirred 8 minutes, at pressure is 0.5MPa, 135 ℃ of temperature, compacting moulding in 30 minutes, have hard wood-based plate outward appearance behind the rubbing down of surface, test the density 1.29g/cm of this material 3, ultimate compression strength 29Mpa, folding strength 11.2Mpa.
Embodiment 5:
Get 50 parts of exsiccant phosphorus slags, 30 parts of manganese slags, 20 parts of municipal refuse incineration slags respectively, 0.1 part of trolamine, 6 parts of caustic soda blend grindings become granularity to account for 89% powder less than 0.08mm; Straw is broken into length earlier less than 5mm; 100 parts in the straw powder of get 106.1 parts of powders, handling, density are 1.27g/ml, modulus is that 30 parts of water glass of 2.3 water glass mix to stir and became compound in 4 minutes, at pressure is hot pressing 10 minutes under 0.1Mpa, 190 ℃ of conditions of temperature, naturally placed 12 hours after the demoulding, test the density 1.15g/cm of this material 3, ultimate compression strength 15Mpa, folding strength 6.7Mpa paints brushing behind the surface grinding, also have wood effect.。
Embodiment 6:
Get 100 parts in flyash, its quality water ratio 8% adds 4 parts of unslaked lime mixing ageings and becomes granularity to account for 91% powder less than 0.08mm with 0.7 part of sodium lignosulfonate, 0.06 part of trolamine, 0.7 part of naphthalene sulfonic acidformaldehyde condensation product, 2 parts of Sodium Silicofluoride blend grindings after 3 hours; Get 107.46 parts of powders, 300 parts of phosphorus slags, density is 1.15g/ml, and modulus is that 2.0 water glass mixes for 50 parts and stirred casting 8 minutes, naturally place the demoulding after 17 hours, be placed in 80 ℃ the sweating room maintenance 12 hours, and diameter arranged behind the surperficial rubbing down in the product less than 8mm pore uniform distribution, ultimate compression strength 62Mpa, folding strength 7.3Mpa has natural volcano stone decoration and skidproof effect.
Embodiment 7:
Prescription and molding mode are with embodiment 6, moulded products was placed in 175 ℃ the steam ambient maintenance 8 hours, diameter was arranged less than 8mm pore uniform distribution, ultimate compression strength 95Mpa behind the surperficial rubbing down in the product, folding strength 12.3Mpa has natural volcano stone decoration and skidproof effect.
Embodiment 8:
With 70 parts in slag, 30 parts of phosphorus slags that replace among the embodiment 6 of municipal refuse incineration slag, adopt the technology of embodiment 6, the goods ultimate compression strength 65Mpa of acquisition, folding strength 7.3Mpa also has the lithotome decorative effect behind the rubbing down.

Claims (1)

1, a kind of production method of low-temperature ceramic stone, it is characterized in that: the component of this material is waste residue, properties-correcting agent, promotor, tensio-active agent, its prescription is for handling waste residue: original state waste residue: properties-correcting agent: promotor: tensio-active agent=100: 30-600: 10-50: 0.5-7: 0.03-2.0
1), to handle waste residue or original state waste residue be in cullet, glass fibre waste residue, flyash, phosphorus slag, metallurgical slag, the municipal refuse incineration slag one or more,
2), properties-correcting agent is the aqueous solution of water glass, density is 1.30-1.52g/ml, modulus is 3.7-2.0,
3), promotor is in calcium silicofluoride, Sodium Silicofluoride, potassium silicofluoride, the caustic soda one or more,
4), tensio-active agent is in trolamine, calcium lignin sulphonate, sodium lignosulfonate, sulfonated melamine compound resin, the naphthalenesulfonate one or more,
The above-mentioned materials of the side of preparing is finished by following production stage:
1), waste residue handles: used waste residue amount to water ratio if greater than 5%, need to add the unslaked lime that waste residue contain quality 30-50%, and mix ageing 1-12 hour; If amount to water ratio and be less than or equal to 5 weight %, just directly use, being granularity through the processing waste residue after the ageing processing through grinding accounts for the powder of 85%-100% less than 0.08mm, becomes mixed powder with the tensio-active agent that measured, promotor mix grinding during grinding,
2), compound preparation: mixed powder adds the original state waste residue and properties-correcting agent is mixed into compound,
3), moulding: when moisture content in the compound during less than 20 weight %, compression moulding, forming pressure 0.1-3.0MPa, hot pressing temperature is 60-198 ℃, and the dwell time is 5-55 minute, when moisture content in the compound during more than or equal to 20 weight %, with vibrating, extrude or casting
4), maintenance: it is in 65-175 ℃ the wet-hot steam environment maintenance 6-36 hour that moulded products is placed after 12-36 hour in temperature naturally again,
5), drying: after the goods maintenance is finished, adopt air-dry, the sun to shine or baker carries out drying and dehydrating, when water ratio becomes work in-process during less than 5 weight %,
6), work in-process polish flat after super-dry, the mixture ornament layer of forming with unsaturated polyester resin, mineral filler, solidifying agent and setting accelerator carries out coating processing, treat surface solidification after, polish, become product.
CNA2007101375847A 2005-07-29 2005-07-29 Method for producing low-temperature ceramic stone Pending CN101100365A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775121A (en) * 2012-08-23 2012-11-14 南京大学 Method for preparing inorganic polymeric material by using waste glass as active aggregate
CN104177056A (en) * 2014-09-03 2014-12-03 武汉大学 Silicon dioxide-based compound supramolecular cementing material and preparation method and application thereof
CN105034125A (en) * 2015-06-12 2015-11-11 江苏兰蒂斯木业有限公司 High-abrasion-resistance cement template and preparation method thereof
CN108840617A (en) * 2018-08-30 2018-11-20 梁钟瑞 Utilize the nano inorganic stone slab and its production method of flyash

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775121A (en) * 2012-08-23 2012-11-14 南京大学 Method for preparing inorganic polymeric material by using waste glass as active aggregate
CN104177056A (en) * 2014-09-03 2014-12-03 武汉大学 Silicon dioxide-based compound supramolecular cementing material and preparation method and application thereof
CN104177056B (en) * 2014-09-03 2016-03-02 武汉大学 A kind of silicon-dioxide base complex supramolecule gelling material and its preparation method and application
CN105034125A (en) * 2015-06-12 2015-11-11 江苏兰蒂斯木业有限公司 High-abrasion-resistance cement template and preparation method thereof
CN108840617A (en) * 2018-08-30 2018-11-20 梁钟瑞 Utilize the nano inorganic stone slab and its production method of flyash

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Open date: 20080109