CN106588117A - Anti-radiation functional aggregate prepared from Cr-containing and Zn-containing electroplating sludge - Google Patents

Anti-radiation functional aggregate prepared from Cr-containing and Zn-containing electroplating sludge Download PDF

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Publication number
CN106588117A
CN106588117A CN201611142289.6A CN201611142289A CN106588117A CN 106588117 A CN106588117 A CN 106588117A CN 201611142289 A CN201611142289 A CN 201611142289A CN 106588117 A CN106588117 A CN 106588117A
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proof function
aggregate
radiation proof
crystal
radiation
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CN106588117B (en
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丁庆军
刘勇强
王承
张杨
耿春东
刘凯
徐意
石华
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • 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
    • C04B28/04—Portland cements
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/1325—Hazardous waste other than combustion residues
    • C04B33/1327—Hazardous waste other than combustion residues containing heavy metals
    • 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
    • C04B33/00—Clay-wares
    • C04B33/32—Burning methods
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • 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
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
    • 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
    • C04B2111/00482—Coating or impregnation materials
    • 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
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
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  • Dispersion Chemistry (AREA)
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  • Treatment Of Sludge (AREA)

Abstract

The invention discloses an anti-radiation functional aggregate prepared from Cr-containing and Zn-containing electroplating sludge. By means of heavy metal elements including Cr and Zn, the anti-radiation functional aggregate has the beneficial effect that the anti-radiation functional aggregate has good shielding performance for high-energy rays, and a regenerated aggregate can have good anti-radiation performance; pulp wrapping processing is conducted on the regenerated aggregate through a vacuum stirring technology, and the surface structure of the aggregate is optimized; ultrahigh performance processing is conducted on the aggregate, subjected to pulp wrapping, through autoclaved curing, and the chemical property, the shielding performance and the heavy metal ion solidification effect of the anti-radiation functional aggregate are improved. The anti-radiation functional aggregate solves the problem that the uniformity of natural high-density ore anti-radiation concrete is poor, meanwhile, a large amount of heavy-metal-containing industrial sludge can be consumed, and the important significance in preparation of anti-radiation concrete and processing of the industrial sludge is achieved.

Description

It is a kind of to be gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge
Technical field
The invention belongs to building material field, and in particular to a kind of using the radioprotective work(prepared containing Cr, Zn electroplating sludge Can gather materials and preparation method thereof.
Background technology
The enterprises such as the battery industry, Surface Processing Industry of China are numerous, because domestic household electrical appliances and electronic equipment update Rapidly, the industries such as the plating of China are caused to develop rapidly, the environmental protection for being treated as protrusion of the trade waste such as electroplating sludge is difficult Topic.Sludge and waste residue produced by electroplating industry is the mixed type garbage rich in various heavy metal components, is that hazardness is larger One of trade waste, more than 400,000 tons of its annual emissions.And content of beary metal is very high contained by electroplating sludge, Cr therein, Zn heavy metal elements respectively up to 13%, 4% or so, the heavy metal of this kind of sludge discharge every year up to more than 100,000 tons, to people Digestive tract, respiratory tract, skin of body etc. have harm, and to the living environment of the mankind threat is caused.
Now, the development of nuclear science technology and the utilization of nuclear energy is 20th century one of the greatest achievement of the mankind, is there is spoke The protection body that needing, shielding radioactive ray is set is penetrated around the structures in source, and radiation shield concrete relies on its excellent ray screen Performance, endurance quality and mechanical property are covered, is built in hospital, nuclear power station and some nuclear screening of scientific research institution with nuclear facilities Build and more and more important effect is played in material.It is that the radiation shield concrete for gathering materials is with barite that at present China is widely used It is main, but there is problems with：First, thickness is done using highdensity natural crystal (barite, magnetic iron ore or limonite ore) Gather materials, although the concrete of preparation has certain shielding ray performance, however, due to the bulk density of natural high-density aggregate it is remote More than cement slurry, the free settling isolation in concrete vibrating construction, poor operability of constructing；Second, it is limited to natural highly dense The density gathered materials of degree is big and the characteristics of universal low intensity, it is generally relatively low with the radiation shield concrete intensity that it is prepared, be used for Nonload bearing element；3rd, these density are larger, and the natural crystal reserves with radioprotective characteristic are limited, it is impossible to meet increasingly The engineering demand of growth, should not use in a large number.
The content of the invention
It is an object of the invention to provide a kind of gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge, it has Excellent shielding property and mechanical property, alternative traditional natural high density Ore gathers materials, and solves traditional radioprotective coagulation Alpha ray shield weakness zone problem caused by native homogeneity is bad, while a large amount of industrial sludges containing heavy metal that can dissolve, have Important economy and environmental benefit.
To achieve these goals, the technical solution used in the present invention is：
A kind of to be gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge, it includes regenerated aggregate and is coated on it The cement mortar shell on surface；The regenerated aggregate is formed by following components is sintered, and mass percent is shared by each component：Plating Sludge powder 49～56%, shale 25～33%, metakaolin 14～22%, flux 1～4%；The cement mortar shell by with The following group lease making mixing, solidification are formed, and mass percent is shared by each component：Cement 62～69%, silicon ash 8.3～12.4% is swollen Swollen dose 5.3～8.8%, water 12.5～16.0%, water reducer 1.4～2.0%.
According to such scheme, the electroplating sludge Jing containing Cr, Zn heavy metal that the electroplating sludge powder is discharged by electroplating industry It is obtained after air-drying, wherein Cr2O3Mass content >=25%, mass content >=15% of ZnO, moisture content≤4%.
According to such scheme, the shale be shale mining it is broken after particle diameter≤4.75mm granules, wherein SiO2 Mass content >=55%, Al2O3Mass content >=20%, loss on ignition≤10%.
According to such scheme, the metakaolin specific surface area >=15000m2/ kg, SiO2Mass content >=40%, Al2O3Mass content >=30%.
According to such scheme, the preparation method of the flux is as follows：1) Borax is dissolved in 95～100 DEG C of water, Filter to obtain settled solution；2) sulphuric acid that mass concentration is 10～20% is added dropwise in gained settled solution under agitation Solution, until there is crystal to separate out, then controls the rate of addition of sulfuric acid solution, it is ensured that and the pH value of gained mixed liquor maintains 4～ 5, treat that crystal is all separated out, sequentially pass through filter, be dried 1.5～2 hours to obtain boric acid crystal at a temperature of 60～70 DEG C；3) by gained boron Acid crystal is heated under vacuum 300～400 DEG C of 0.5～1h of calcining, is then heated to 500～600 DEG C of 1～2h of calcining, Finally heated to 800～900 DEG C are incubated 1～2 hour, and natural cooling obtains glassy state B2O3Crystal；4) by glassy state B2O3Crystal, Na2O、K2O mix homogeneously, preheats 0.5～1h at a temperature of 500～600 DEG C, and 2～3 are incubated under 1120～1180 DEG C of high temperature Hour, most after Jing water quenchings chilling obtain B2O3-Na2O-K2O eutectics, the glassy state B2O3Crystal, Na2O、K2Quality hundred shared by O Point ratio is：Glassy state B2O3Crystal 40～50%, Na2O 25～35%, K2O 15～25%；5) by B2O3-Na2O-K2O eutectics It is ground, obtains final product the cosolvent.
In such scheme, step 1) described in the quality of boric acid and the ratio of the volume of water be 1:(1.6～2.8) g:ml.
In such scheme, step 3) described in vacuum condition be vacuum≤300Pa.
According to such scheme, the cement is P.O 42.5 or the Portland cements of P.O 52.5.
According to such scheme, the silicon ash specific surface area >=17000m2/ kg, SiO2Mass content >=85%, 28d is active Index >=104%.
According to such scheme, the extender be MgO type extenders, specific surface area >=200m2/kg。
According to such scheme, the water reducer be common polycarboxylic acid water reducing agent, solid content >=50%, water-reducing rate >= 25%.
According to such scheme, the water is ordinary tap water.
According to such scheme, the sintering process of the regenerated aggregate comprises the steps：1) each component is weighed by proportioning, respectively Mass percent is shared by component：Electroplating sludge powder 49～56%, shale 25～33%, metakaolin 14～22%, flux 1 ～4%；By each raw material for weighing mixing, grinding, pelletize is then carried out, particle diameter is 5～10mm, and moisture content is 16～20%；2) Pelletize gained balling-up is preheated into 30～40min at 500～600 DEG C, 40～50min is calcined at 1020～1080 DEG C, most Naturally cool to room temperature in atmosphere afterwards, obtain regenerated aggregate.
The preparation method that radiation proof function described in such scheme gathers materials, it comprises the steps：1) weigh according to the following ratio Cement mortar each component, mass percent shared by each component is：Cement 62～69%, silicon ash 8.3～12.4%, extender 5.3～ 8.8%, water 12.5～16.0%, water reducer 1.4～2.0%, by regenerated aggregate with cement, silicon ash, the extender for weighing true 2～4min of dry mixing under empty condition, adds water and water reducer, continues at 5～10min of stirring under vacuum state, and gained is wrapped up Uniformly paving is spilt for the regenerated aggregate of cement mortar shell, it is to avoid cementing, and 1～2d of natural curing occurs between gathering materials；2) by step 1) institute Product conserve after 4～6h under conditions of 180～200 DEG C, 1～2MPa and is cooled to room temperature, obtain final product described electric using Cr, Zn is contained Radiation proof function prepared by plating sludge gathers materials.
In such scheme, the regenerated aggregate is 1 with the mass ratio of cement mortar:(0.25～0.55).
In such scheme, step 1) described in vacuum condition be 2kPa～5kPa.
In such scheme, the cladding thickness of the cement mortar shell is 0.5～1.0mm.
The principle that adopts of the present invention for：
(1) gather materials shielding property：From electroplating industry, (plating is dirty for the trade waste containing heavy metal elements such as Cr, Zn Mud) used as the sintering raw material that gathers materials, Cr, Zn heavy metal element atomic nucleus therein and electron outside nucleus and gamma-rays occur complicated Material effect (mainly includes：Photoelectric effect, Compton scattering and pair effect)；In gamma-rays by the same of absorbing material When, γ photons can occur material effect with the atomic nucleus in material interior atoms structure and electron outside nucleus, and transmitted intensity declines Subtract, so that gained regenerated aggregate shows shielding property.
(2) flux：The present invention reduces the firing temperature that gathers materials, it is to avoid the loss of heavy metal ion by adding flux, The regenerated aggregate higher so as to obtain Cr, Zn heavy metal ion content.Concrete mechanism is to gather materials in sintering process, Al2O3、SiO2 For the firing temperature that refractory components, its decision gather materials.B in flux2O3、Na2O、K2O under high temperature action, wherein B, Na, K Plasma can be with Al2O3、SiO2Form the solid solution of low melting point；Simultaneously SiO can be entered2Si-O tetrahedral structures in, make original Tetrahedral structure change, be no longer completely closely to connect, while decompositing free oxygen, cause SiO2Stability itself Decline, so as to reduce firing temperature (130～150 DEG C of firing temperature can be reduced).Effectively prevent heavy metal ion dissolution or Volatilization.
(3) regenerated aggregate burns till：From Cr containing heavy metal element, the electroplating industry sludge of Zn, by shale, metakaolin Correction to Si, Al mineral so that in the matrix material of regenerated aggregate based on Si, Al, Cr, Zn element；Now, shale and partially Substantial amounts of Al in Kaolin2O3、SiO2It is offer intensity of gathering materials in calcination process as refractory components, prevents regenerated aggregate from forging Subside during burning, form fine and close inner core；Si simultaneously in Cr, Zn heavy metal element and shale, metakaolin, Al mineral facies melt compoundeds so as to be solid-solubilized in Al2O3、SiO2In the solid solution of formation, resistant mineral phase is formed, it is to avoid sintered The dissolution of heavy metal in journey, improves the alpha ray shield performance of functional aggregate.
(4) regenerated aggregate Surface coating：The present invention can effectively make up sintering institute using cement mortar surface Hardening Treatment technique The performances such as the surface defect (hole, micro-crack etc.) that regenerated aggregate is easily produced, intensity, the durability that raising is gathered materials are obtained, and can be carried Height gathers materials apparent density, and concrete mix service behaviour is poor caused by the density that solves the problems, such as typically manually to gather materials is less；Together When, the present invention adopts vacuum stirring technique (vacuum is 2kPa～5kPa), and gelling slurry can be avoided to introduce bubble in stirring, Hole in slurry is made only from evaporation of water, so as to the porosity of the slurry that reduces being gelled, improve gelling slurry degree of compaction and Intensity；In addition vacuum stirring can be such that cement slurry is more easy in the middle of the hole and micro-crack on regenerated aggregate surface, and improve again The interface transition layer that life is gathered materials between cement slurry, further improves the degree of compaction that radiation proof function gathers materials；One is mixed simultaneously Quantitative MgO type extenders so as to activity, hydrated product Mg (OH) are played under autoclaved condition2Filling slurry hole, and be interspersed in Between aquation gelling slurry, increase deflation resistance, compensation contraction is played to slurry, improve the boundary between slurry and clinker aggregate Face transition zone, so as to improve the intensity and shielding property of gained functional aggregate.
(5) steam press maintenance：The present invention is improve between hydrated cementitious and cement and silicon ash using steaming pressuring curing process Pozzolanic reaction degree, and the activity of MgO type extenders is fully excited, increased gelling slurry C-S-H gels, Ca (OH)2、Mg (OH)2Deng the quantity of hydrated product, gelling slurry pore structure is improved；Meanwhile, autoclaved condition can promote high alkalinity C-S-H to knot The zeolites products such as the good tobermorite of brilliant degree are converted, and make hydrated product structure more stable, from a physical angle reinforcing huge sum of money The solidification effect of category ion；Regenerated aggregate is carried out wrapping up in steam press maintenance is carried out after slurry is processed, can be big while raising aggregate strength Width improves gelling slurry and the interface transition layer between gathering materials, and improves the solidification of the heavy metal ion that gathers materials, and increases collection The service life of material, it is to avoid its under arms during cause because of the dissolution of heavy metal ion concrete shielding property decline.
Compared with prior art, the invention has the beneficial effects as follows：
(1) electroplating sludge containing heavy metal element Cr, Zn is fired into into the regenerated aggregate for radiation shield concrete, no The process problem of industrial waste sludge is address only, is conducive to environmental protection, while alternative traditional natural high density Ore collection Material, solves the problems, such as the bad caused alpha ray shield weakness zone of traditional radiation shield concrete homogeneity.
(2) with electroplating sludge powder as primary raw material, using the SiO in shale, metakaolin2、Al2O3There is provided strong to gather materials Degree, is aided with certain calcining system, and Cr, Zn heavy metal ion is solid-solubilized in Si/Al phase solid solution, so that regenerated aggregate Shielding property and intensity are largely increased.
(3) using the B in flux2O3、Na2O、K2O components, can effectively reduce firing temperature, not only avoid heavy metal The dissolution of ion, while meeting the requirement of national energy development strategy.
(4) pre- slurry of wrapping up in is carried out to regenerated aggregate using high-strength cement slurry to process, optimizes regenerated aggregate surface texture, reduce collection The porosity of material, improves its degree of compaction, not only increases the mechanical property and shielding property gathered materials, while solving general artificial collection The less problem of material density, it is ensured that it is suitable with the density of concrete mix rubber cement, so as to improve the even of radiation shield concrete Matter.
(5) extender is applied to the preparation of high-strength cement slurry, its activity is excited with reference to steaming pressuring curing process, using MgO Expansion characteristics compensation gelling slurry aquation during produce volume contraction, so as between solving slurry and gathering materials interface lack Sunken problem, improves the degree of compaction and intensity of synthetic aggravation；Conserved to wrapping up in slurry in advance and gathering materials using steaming pressuring curing system simultaneously, led to Cross improvement cement slurry microstructure composition, reduce slurry porosity, increase its intensity, improve cement slurry and regenerated aggregate it Between interface transition layer, and strengthen the solidification of heavy metal ion of gathering materials, so as to improve intensity that radiation proof function gathers materials, The solidification effect of the performances such as alpha ray shield and heavy metal ion.
Obtained radiation proof function of the invention gathers materials, and property indices are excellent, and apparent density is in 2500kg/m3Left and right, it is single Grain compressive strength >=14.0MPa, linear weak coefficient >=0.24cm-1, it is actual with preferable intensity and shielding property Using value is huge, can be used to prepare high-strength radiation shield concrete.
Description of the drawings
Fig. 1 is the structural representation of the gamma ray shielding experimental provision that embodiment 1～4 is adopted.
Specific embodiment
To make the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, the present invention is entered Row is further described.It should be appreciated that specific embodiment described herein is not used to limit only to explain the present invention The present invention.
In following examples, Surface Treatment Industry relevant enterprise of the electroplating sludge powder in the industry park of Ezhou contains Cr, Zn heavy metal element industrial sludge (electroplating sludge), obtain, Cr after carrying out air-drying2O3Mass content 26.68%, ZnO's Mass content 19.63%, moisture content 3.0%；The shale originates from Yichang City, Hubei Province shale mine, particle diameter≤4.75mm, Wherein SiO2Mass content 57.33%, Al2O3Mass content 24.14%, loss on ignition 8.2%；The metakaolin is by Hangzhoupro Chemical Co., Ltd. of Zhou Chong sections provides, specific surface area 16000m2/ kg, SiO2Mass content 42.89%, Al2O3Quality contain Amount 34.15%；The cement is the new PO42.5 Portland cements of China, and specific surface area is 320m2/kg；The silicon ash by Shanghai Tian Kai silica flours Materials Co., Ltd provides, specific surface area 18000m2/ kg, SiO2Mass content 90%, 28d activity indexs 105%；The MgO type extenders that the extender is produced for Wuhan San Yuan special type building materials limited company, specific surface area 220m2/kg；The water reducer is Jiangsu Subotexin Material Co., Ltd's productionType polycarboxylate water-reducer, Solid content 50%, water-reducing rate 30%；Water adopts ordinary tap water.
The preparation method of the flux is comprised the following steps：
1) distilled water of 550ml is added in magnetic agitation heating kettle, and is heated to 95 DEG C or so, be subsequently adding 250g's Borax, is stirred well to Borax and all dissolves, it is ensured that the temperature of mixed solution is more than 90 DEG C, while solution is filtered, obtains Settled solution；2) adopt acid buret to step 1) obtain settled solution in Deca mass concentration for 15% dilute sulfuric acid, And be slowly stirred, until there is crystal to separate out, now control the addition speed of sulphuric acid, it is ensured that solution ph maintains 4～5, treats crystalline substance Body is all separated out, and surplus solution is filtered, and is then dried 1.5 hours at a temperature of 65 DEG C, obtains boric acid crystal；3) by step 2) Obtained boric acid crystal (260Pa) under vacuum condition, is heated to 350 DEG C of calcining 0.5h, is then heated to 600 DEG C of calcining 1h, It is last to be incubated 2 hours at 800 DEG C, glassy state B is obtained Jing after natural cooling2O3Crystal；4) by step 3) obtained in glassy state B2O3Crystal and Na2O、K2After O is sufficiently mixed uniformly, 1h is preheated at a temperature of 550 DEG C, insulation 3 is little under 1160 DEG C of high temperature When, most after Jing water quenchings chilling obtain B2O3-Na2O-K2Mass percent shared by O eutectics, wherein each component is：Glassy state B2O3 Crystal 45%, Na2O 30%, K2O 25%；5) by step 4) obtained in B2O3-Na2O-K2O eutectics are fully ground, and sieve 70 Mesh, obtains the flux.
Embodiment 1～4
Gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge described in embodiment 1～4, including regenerated aggregate With the cement mortar shell for being coated on its surface；The regenerated aggregate is burnt by electroplating sludge powder, shale, metakaolin, flux Jing Knot is formed；Cement mortar shell is formed with cement, silicon ash, extender, water, water reducer as raw material Jing mixings, solidification, concrete proportioning It is shown in Table 1；Its preparation method comprises the steps：
1) proportioning as described in table 1 weighs the sintering each component that gathers materials, and then each raw material for weighing mixing, grinding are carried out Pelletize, particle diameter is 5～10mm, controls moisture content for 18%；2) pelletize gained balling-up is preheated into 35min at 550 DEG C, then at 50min is calcined at 1060 DEG C, room temperature is finally naturally cooled in atmosphere, obtain regenerated aggregate；3) surface bag is weighed by the proportioning of table 1 Cover and use cement mortar each component, by 100kg regenerated aggregates with the cement, silicon ash, extender for weighing in vacuum stirring pot (vacuum Dry mixing 2min is carried out under 4kPa), water and water reducer is added, to be continued at and stir 8min under vacuum state, gained is wrapped up into cement The regenerated aggregate of slurry carries out uniform paving and spills, it is to avoid cementing, and natural curing 1d occurs between gathering materials；4) by step 3) products therefrom exists 200 DEG C, conserve under conditions of 2MPa and be cooled to room temperature after 6h, obtain final product described using the radioprotective prepared containing Cr, Zn electroplating sludge Functional aggregate.
Whether Cr, Zn heavy metal element can be steady during gathering materials under arms for the checking gained radiation proof function of embodiment 1～4 It is fixed to exist, establishing criteria HJ/T299-2007《Solid waste Leaching leaching method sulfonitric method》Test the radioprotective work( Can be gathered materials the toxicity leaching content of fragment heavy metal element in attack solution.
To verify the gained radiation proof function of embodiment 1～4 gathers materials whether have good shielding property, it is carried out 0.662MeV gamma ray shieldings test (structural representation is shown in Fig. 1), and experimental provision mainly includes：Radioactive source isotope gamma-rays Source, NaI (T1) probes, digitized gamma energy spectrometer.Test sample is placed between detector and radioactive source, 60s timing rays are done Ionization meter；The thickness of sample is measured with slide gauge；The linear weak coefficient of material is carried out with method of least square Calculate.
The performance test results that radiation proof function obtained in embodiment 1～4 gathers materials are shown in Table 2.
Radiation proof function described in the embodiment 1～4 of table 1 gathers materials the addition (kg) of each raw material
The property indices that radiation proof function obtained in the embodiment 1～4 of table 2 gathers materials
The above results show that the apparent density gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge is existed 2500kg/m3Left and right, far below barite apparent density (4200～4600kg/m3), closer to the close of concrete mix slurry Degree, can be more uniformly distributed in radiation shield concrete, make concrete have more preferable homogeneity, strengthen gained function collection Interface performance between material and Behavior of Hardened Cement Paste, and reduce the unit weight of radiation shield concrete；Its linear weak coefficient is higher than 0.24cm-1, With barite (μ=0.24～0.27cm-1) close；Individual particle comprcssive strength >=14.0MPa (barite is 12MPa or so)；Weight Metal leaching concentration meets GB5080.3-2007《Hazardous waste judging standard-leaching characteristic identification》And GB8978-1996《It is dirty Water comprehensive discharge standard》National standard is required.
Above-described embodiment just for the sake of clearly demonstrating the present invention, not to the restriction of embodiment, at the same here without Need also be exhaustive all of embodiment.For the person of ordinary skill of the art, without departing from the present invention Create design on the premise of, amplified it is obvious some improvement and change still in the invention protection domain it It is interior.

Claims (10)

1. it is a kind of using containing Cr, Zn electroplating sludge prepare radiation proof function gather materials, it is characterised in that it include regenerated aggregate and It is coated on the cement mortar shell on its surface；The regenerated aggregate is formed by following components is sintered, quality percentage shared by each component Than for：Electroplating sludge powder 49～56%, shale 25～33%, metakaolin 14～22%, flux 1～4%；The cement mortar Shell is formed by following components Jing mixing, solidification, and mass percent is shared by each component：Cement 62～69%, silicon ash 8.3～ 12.4%, extender 5.3～8.8%, water 12.5～16.0%, water reducer 1.4～2.0%.
2. radiation proof function according to claim 1 gathers materials, it is characterised in that the electroplating sludge powder is arranged by electroplating industry The electroplating sludge containing Cr, Zn heavy metal put is obtained Jing after air-drying, wherein Cr2O3Mass content >=25%, the quality of ZnO contains Amount >=15%, moisture content≤4%.
3. radiation proof function according to claim 1 gathers materials, it is characterised in that the shale is broken for shale mining Particle diameter afterwards≤4.75mm granules, wherein SiO2Mass content >=55%, Al2O3Mass content >=20%, loss on ignition≤ 10%.
4. radiation proof function according to claim 1 gathers materials, it is characterised in that and the metakaolin specific surface area >= 15000m2/ kg, SiO2Mass content >=40%, Al2O3Mass content >=30%.
5. radiation proof function according to claim 1 gathers materials, it is characterised in that the preparation method of the flux is as follows： 1) Borax is dissolved in 95～100 DEG C of water, filters to obtain settled solution；2) under agitation in gained settled solution by It is 10～20% sulfuric acid solution to be added dropwise to mass concentration, until there is crystal to separate out, then controls the rate of addition of sulfuric acid solution, The pH value for ensureing gained mixed liquor maintains 4～5, treats that crystal is all separated out, and sequentially passes through filter, dry at a temperature of 60～70 DEG C Obtain boric acid crystal within 1.5～2 hours；3) gained boric acid crystal is heated under vacuum 300～400 DEG C of 0.5～1h of calcining, 500～600 DEG C of 1～2h of calcining are then heated to, finally heated to 800～900 DEG C are incubated 1～2 hour, and natural cooling obtains glass State B2O3Crystal；4) by glassy state B2O3Crystal, Na2O、K2O mix homogeneously, preheats 0.5～1h at a temperature of 500～600 DEG C, then Under 1120～1180 DEG C of high temperature be incubated 2～3 hours, most after Jing water quenchings chilling obtain B2O3-Na2O-K2O eutectics, the glass Glass state B2O3Crystal, Na2O、K2Mass percent is shared by O：Glassy state B2O3Crystal 40～50%, Na2O 25～35%, K2O 15～25%；5) by B2O3-Na2O-K2O eutectics are ground, and obtain final product the cosolvent.
6. radiation proof function according to claim 1 gathers materials, it is characterised in that the silicon ash specific surface area >=17000m2/ Kg, SiO2Mass content >=85%, 28d activity index >=104%.
7. radiation proof function according to claim 1 gathers materials, it is characterised in that the extender is MgO type extenders, than Surface area >=200m2/kg。
8. radiation proof function according to claim 1 gathers materials, it is characterised in that the sintering process of the regenerated aggregate includes Following steps：1) each component is weighed by proportioning, mass percent shared by each component is：Electroplating sludge powder 49～56%, shale 25 ～33%, metakaolin 14～22%, flux 1～4%；By each raw material for weighing mixing, grinding, pelletize, grain are then carried out Footpath is 5～10mm, and moisture content is 16～20%；2) pelletize gained balling-up is preheated into 30～40min at 500～600 DEG C, then at 40～50min is calcined at 1020～1080 DEG C, room temperature is finally naturally cooled in atmosphere, obtain regenerated aggregate.
9. the preparation method that radiation proof function described in any one of claim 1～8 gathers materials, it is characterised in that comprise the steps： 1) cement mortar each component is weighed according to the following ratio, and mass percent shared by each component is：Cement 62～69%, silicon ash 8.3～ 12.4%, extender 5.3～8.8%, water 12.5～16.0%, water reducer 1.4～2.0%, by regenerated aggregate and the water for weighing Mud, silicon ash, extender 2～4min of dry mixing under vacuum, adds water and water reducer, to continue at and stir 5 under vacuum state ～10min, carries out the regenerated aggregate that gained wraps up cement mortar uniform paving and spills, it is to avoid cementing, and natural curing 1 occurs between gathering materials ～2d；2) by step 1) products therefrom conserves after 4～6h under conditions of 180～200 DEG C, 1～2MPa and is cooled to room temperature, obtain final product It is described to be gathered materials using the radiation proof function prepared containing Cr, Zn electroplating sludge.
10. preparation method according to claim 9, it is characterised in that step 1) described in vacuum condition be 2kPa～ 5kPa。
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CN107117843A (en) * 2017-06-06 2017-09-01 浙江工业大学温州科学技术研究院 A kind of method that nature of glass solidifies electroplating sludge
CN108658488A (en) * 2018-05-03 2018-10-16 宋俊芳 A kind of radiation protection thermal insulation board and preparation method thereof
CN109333828A (en) * 2018-11-10 2019-02-15 山东交通学院 Regeneration concrete intensifying method
CN109333828B (en) * 2018-11-10 2023-09-08 山东交通学院 Method for reinforcing recycled concrete
CN111847944A (en) * 2020-07-23 2020-10-30 中国建筑科学研究院有限公司 Ferrochromium slag for concrete aggregate and preparation method thereof
CN111847939A (en) * 2020-08-05 2020-10-30 中国建筑材料科学研究总院有限公司 Aggregate with irradiation resistance function and preparation method and application thereof
CN111847940A (en) * 2020-08-05 2020-10-30 中国建筑材料科学研究总院有限公司 Aggregate with irradiation resistance function and preparation method thereof, irradiation-resistant concrete and preparation method thereof
CN113336460A (en) * 2021-06-28 2021-09-03 武汉理工大学 Functional aggregate for radiation-proof concrete and preparation method thereof
CN114573299A (en) * 2022-03-25 2022-06-03 安徽建筑大学 Anti-cracking and anti-impact ultrahigh-performance radiation-proof concrete and preparation method thereof
CN115572089A (en) * 2022-10-14 2023-01-06 武汉理工大学 Phosphogypsum aggregate, radiation-proof ultrahigh-performance concrete and preparation method thereof
CN115572089B (en) * 2022-10-14 2023-08-18 武汉理工大学 Phosphogypsum aggregate, radiation-proof ultra-high-performance concrete and preparation method thereof

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