CN103274658A - Industrial waste residue and solid danger refuse resource utilization method - Google Patents
Industrial waste residue and solid danger refuse resource utilization method Download PDFInfo
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- CN103274658A CN103274658A CN2013100126522A CN201310012652A CN103274658A CN 103274658 A CN103274658 A CN 103274658A CN 2013100126522 A CN2013100126522 A CN 2013100126522A CN 201310012652 A CN201310012652 A CN 201310012652A CN 103274658 A CN103274658 A CN 103274658A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides an industrial waste residue and solid danger refuse resource utilization method, which comprises the following steps: mixing the waste residue and the danger refuse of different pH values together, carrying out acid and alkali adjustments with chemical and physical synergism, neutralizing, balancing the pH valve to neutral for stabilization. The consolidation agent is used for rapid consolidation of waste residue particles, thereby fixing the toxic heavy metal ions and pathogen inside, and the leaching toxicity does not exceed standard and the hidden trouble of harm is eliminated. The product can replace clay for manufacturing wall material and member, and the resource can be integratedly utilized. And the ecological environment is protected. The invention has the advantages of substantial social, environment and economic benefits, and can be used in the continuous development industry in the circular economy technology field.
Description
(1) technical field the invention belongs to field of environment engineering technology, relates to a kind of industrial residue, solid dangerous waste comprehensive utilization method.
(2) background technology solid waste (comprising solid dangerous waste) refers to the solid gunk that abandons in human being's production, the life process, and it is the product of human material progress.A large amount of solid waste enter environment, not only take a large amount of soils, and, heavy metals such as mercurous, the chromium that contains in the solid waste, lead, nickel, copper, aluminium, tin, vanadium, molybdenum, iron, manganese and virus, germ, pathogeny body, pollute surrounding environment, destroy the eubiosis, bring serious Health hazard to the mankind.
Reclamation of solid wastes utilizes, and exactly solid waste is considered as secondary resource, makes them as the starting material recycling.At present, existing many countries by economic leverage and mandatory administration means, encourage and support the development and application of reclamation of solid wastes technology.
On April 1st, 1996 was played execution " People's Republic of China's prevention and control of environmental pollution by solid wastes method " in by China.Wherein, at first established " minimizing, innoxious, resource utilization " principle of solid waste pollution control, established the principle of solid waste being carried out Whole Course Management simultaneously, and established the basic framework of Solid Waste Management of Our Country system according to these principles.
Reclamation of solid wastes needs series of effective technology and means, and supporting with it facility is arranged.Also there is bigger gap in China compared with developed countries in this field, many places or industrial and mining enterprises are not to can not find suitable development technique, are exactly that technology or facility can not pass.Perhaps also stay in the blindness state that huddles of disorderly arranging.Therefore, strengthen development research and the through engineering approaches of reclamation of solid wastes technology are used, the control environmental pollution causes the harm to human health, is the major issue of not tolerating current quarter.
In general, be the basic skills of safe handling harm refuse with the method for cement stable curing, in overbasic silicate cement system hydration process, some harmful heavy metals by with the main aquation phase of cement CSH (CaOSiO
2HH
2O) physics chemical action, in bond being stabilized in the cement solidification matrix.In view of cement solidification method has economy, advantage such as easy to operate, this solidification matrix Hazardous wastes abroad is used widely in handling.Simultaneously, for high-voidage, the hypertonicity that overcomes traditional cement solidification matrix reaches problems such as heavy metals immobilization efficient such as lead, arsenic, mercury, chromium are low, also take up to do the research work of multiple modified version cement solidification substrate formula.
The patent of external modified version cement solidification matrix, mainly concentrate on the invention of four classes: (1) silicate cement admixture blended material (as siliceous, slag, flyash) series, (2) silicate cement and the compound series of water glass additive, (3) silicate cement and the compound series of some reductive agents, the compound series of the siliceous blended material of (4) lime.But it is still unresolved in the pretreated actual engineering of Hazardous wastes landfill to use these follow-on cement solidification matrix; 1. the solidification matrix increase-volume is higher than imitating.2. solidification matrix exists the problem of the anion radical solidification effect difference of heavy metal high-valence cationic, and recycling is difficult to realize.
(3) summary of the invention
For addressing the above problem, the purpose of this invention is to provide a kind for the treatment of of wastes with processes of wastes against one another, the method for the industrial residue of low cost production, solid dangerous waste recycling, recovery industrial residue, solid dangerous waste carry out recycling.Reduce them to pollution and the harm of environment: according to new wall material should " joint soil be economized ground, sharp useless, environmental protection " principle, be main raw material with solid waste, manufacture novel wall brick and building slab.
The present invention is achieved in that the method for a kind of industrial residue, solid dangerous waste recycling, and this method comprises the processing step of following order:
1, mixes stirring technique: adopt endless belt conveyor under the thing amount control of material autmatic measuring device and liquid meter measuring device, the water of the solid dangerous waste, 0～20% (weight percent) of the industrial residue, 10～80% (weight percent) of 40～80% (weight percents) is added to SB series twin-shaft mixer stirs 2～5mim, be mixed into behind the mixing sludge standby;
2, detect pH value: step 1 mixing sludge is carried out pH value detect, the pH value of the mixing sludge that records 7.5 below is being acidic mixed mud.PH value more than 9 is being alkaline mixing sludge;
3, mix stone roller and grind step: acidity or the alkali mixing sludge of step 2 are mixed with following (weight percent) component: adopt screw machine to carry, with 10～80% acid or alkaline mixing sludge, 0～5% stablizer, 10～30% unslaked lime (CaO), 0～10% gypsum powder (CaSO
42H
2O), 0～15% water, under material autmatic measuring device and the control of liquid flow mearuement implements amount, be added to XJ-II series and load in the planet machine, mix to grind and grind.It is 7.5～9 neutral compound that stone roller is ground into pH value.Its technology controlling and process comprises five aspects: the selection of (1) grinding pressure.If the coarse aggregate volume is bigger in the material that the employing granularity is big or the thin material, the hardness of material is little and frangible, pressure can reduce: the granularity of (2) fines is more little, the coarse fodder volume is more few, or material is very hard, and friability is very poor, then should select big pressure, by load rows 3 star machine rules, can regulate loading force: (3) mixing of materials mode selects to select for use XJ-II series to load unique hybrid mode that the planet machine is held: (4) grind the control of the time of grinding.The each stone roller ground time control in 5～15min regulation range: the control of (5) feeding quantity.Each feeding quantity control is at 400～450kg;
3, digestion step: step 3 is carried out material digestion through grinding the neutral compound grind, being delivered in the continous way slaking silos, material is fluid type and flows in slaking silos, and neutral compound is by the continuously feeding of its top feed mouth, the continuous discharging in bottom.The load of the discharging equipment at the bottom of the storehouse, be adjusted to make material in slaking silos by the traveling time that is fed to discharging, be equivalent to advance the contained calcium oxide of material digestion required time.Digestion time is 1～6h.Utilize the waste vapour of autoclave to add thermal material, heat, humidification.Temperature keeps more than 40 ℃ in the storehouse.Discharging moisture can not be too high, and more the end is more good under the prerequisite that guarantees the required moisture of digestion.Through postdigestive material, become the digestion material;
4, whole whipping step: with the digestion material of step 4 gained, under the control of material autmatic measuring device, be quantitatively transferred to SB series twin-shaft mixer and solidifying agent, an amount of magnetized water mixing and stirring, its weight percent is respectively digestion material 80～90%, solidifying agent 5～20%, magnetized water is an amount of.Twin-shaft mixer is equipped with materials-stored box.Configuration CH～33 type magnetizing apparatuss.The technical requirements of magnetization hot water is: 60～100 ℃ of water temperatures, magnetic strength 1500～3000GS, flow velocity 60～80Cm/S.Churning time detects according to material at random and decide, and the present invention controls at 3～7min producing the churning time of implementing.Water ratio control is made the base material between 15～20%, the input materials-stored box is standby;
5, punch steps; In the base material of step 5 gained is framed from the punching press of the quantitative input hydraulic pressure brick of materials-stored box machine, strike out solid brick, change the goods blank of body of wall hollow brick, square floor tile, pavement bricks, the road side road stone that the framed and mould of punching press just can the punching press all size and the material of construction such as storm pavement of reclaiming fields from the sea;
5, maintaining process step: (1) precuring: adopt nature precuring method, two kinds of methods of damp and hot precuring method.Room temperature places brick or goods blank on the steam-cured car adopting the natural curing method more than 10 ℃, is parked in natural curing in the indoor physical environment, and the time is 0～90h, and room temperature can not guarantee to adopt damp and hot precuring method more than 10 ℃ the time.Brick or goods blank are put on the steam-cured car, be parked in close the doors and windows indoor after, slowly feed steam, insulation precuring 5～8h, the precuring temperature is 40～50 ℃.(2) steam press maintenance: will be drawn in Φ 1650mm or the Φ 2000mm autoclave steam-cured with windlass through the steam-cured car that brick or goods blank are housed of precuring.Autoclave operating pressure and temperature according to product design intensity, are divided into pressure 0.81.01.3MPa.Temperature is 174.5 ℃, 183.2 ℃, 194.1 ℃.Steam the compacting degree; Preheating 3～4n under the wet heat condition about 50 ℃ is warmed up to 174.5 ℃ (0.8MPa pressure) in 2～3n, constant temperature (174.5 ℃) 5～8h, cooling 2～3h (going out the still temperature difference less than 80 ℃).
An air inlet reducing valve is arranged at the top of autoclave, ceaselessly discharges small amount of steam, with pipeline tail vapour is imported slaking silos, and material is heated.
The described industrial residue of step 1 refers to the active waste residue of phenotype or/and the active waste residue of latent type; The active waste residue of phenotype is slag, slag, phosphorus slag, red mud, shrend copper ashes, ferroalloy slag and silicon manganese slag.The active waste residue of latent type is that artificial sand, the building waste that flyash (II, III level ash), coal gangue burning slag, slag, electric furnace slag, phosphogypsum, carbide slag, pyrite cinder, CHARACTERISTICS OF TAILINGS SAND, the useless molding sand of casting, quartzose barren rock and tankage are pulverized pulverized slag.
The active waste residue of phenotype refers to not only contain active SiO
2With active A l
2O
3, and contain activity of cement mineral C
2S and C
3The waste residue of S, these waste residues are because containing C
2S and C
3S and can directly hardening, but a large amount of active SiO that contains
2And Al
2O
3Activeconstituents is direct aquation (sclerosis) but, still needs exciting jointly of activator and CaO, so the exciting agent that the active waste residue of phenotype also still needs to contain in the solidifying agent excites its activity, and is necessary, otherwise, have only C
2S and C
3S plays a role, and SiO
2With Ai
2O
3Then can not play a role.
The active waste residue of latent type refers to only contain active SiO
2With active A l
2O
3, and do not contain activity of cement mineralogical composition (Dicalcium Phosphate (Feed Grade)) and C
3The waste residue of S (silicic acid three) is so the activity of the active waste residue of latent type only just can show under CaO and the common situation about existing of exciting agent.
The active waste residue of the active waste residue of phenotype and latent type can use separately, also can use by two or more mix and match SiO separately or in the waste residue of collocation back
2, Al
2O
3, CaO content sum should be greater than 70%, sulfur oxide content should be less than 3%.Its granularity requirements is for being not more than 5mm.
The chemical ingredients of the active waste residue of part phenotype sees Table shown in-1:
The chemical ingredients of the active waste residue of the latent type of part sees Table shown in-2:
Table one 1: the chemical ingredients of the active waste residue of part phenotype
| Project | SiO 2 | Al 2O 3 | F 2O 3 | CaO | Na 2O | MqO | P 2O 3 | K 2O | TlO 2 | MnO | FeO | F-CaO | Other | Loss on ignition |
| Slag | 55.8 | 27.3 | 8.6 | 3.6 | 0.8 | 2.8 | 1.2 | 2.9 | 0.2 | 4.7 | ||||
| Slag | 33.56 | 14.56 | 1.46 | 41.73 | 0.75 | 1.13 | 14.3 | |||||||
| Red mud | 19.35 | 11.10 | 7.10 | 50.00 | 2.30 | 10.00 | 21.10 | |||||||
| Silicon manganese slag | 31.5 | 11.4 | 1.5 | 45.6 | 9.1 | 5.2 | 17.3 | |||||||
| Ferroalloy slag | 37.64 | 1.05 | 5.08 | 0.11 | 35.68 | 0.20 | 0.24 | 0.9 |
[0026]Table-2: the chemical ingredients of the active waste residue of the latent type of part
The active waste residue of phenotype and latent type activity waste residue are different because of the place of production, and chemical ingredients has nothing in common with each other, and index differs greatly.
From table-1 and table-2 as seen, the main chemical compositions of the active waste residue of phenotype and latent type activity waste residue is SiO
2, AI
2O
3And CaO.
The described solid dangerous waste of step (1) refers to list in " national Hazardous wastes register " (2008) or has one or more the solid waste of dangerous feature such as corrodibility, inflammableness, reactivity and infectivity according to what " Hazardous wastes authentication technique standard " HJ/T298-2007 of national regulation assert.They are shown in the table-3.
Table-3: Hazardous wastes classification, source and refuse title
Continuous table:
Annotate: be numbered the hazardous material numbering in " national hazardous substance register " in the table
Incineration disposal residue-incineration disposal residue and dust of " dangerous register " HWl8, be burning slag and the MSW flying dust after industry or consumer waste incineration are disposed, contain heavy metals such as many harmful lead, chromium, zinc and mercury, burn slag, the unprocessed landfill that gives of MSW flying dust as these, the seepage of landfill liquid in underground will constitute serious threat to the ecosphere of human survival.
The main chemical compositions of certain garbage incinerating power plant MSW flying dust is referring to shown in the table-4:
Table-4: the main component of certain garbage incinerating power plant MSW flying dust
| Chemical ingredients | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O | Na 2O | SO 3 | Cl- | Loss on ignition |
| Content (%) | 45.05 | 15.84 | 4.27 | 13.28 | 3.36 | 2.81 | 2.26 | 3.23 | 1.72 | 8.28 |
From the table-4 visible MSW flying dusts main component be SiO
2, Al
2O
3And CaO.
Each burning electricity generation factory difference because burning away the refuse of various places, the chemical ingredients of MSW flying dust is had nothing in common with each other.
" Hazardous wastes register " HW21 contains chromium refuse-chromium containing electroplating mud, and thing coordinates and is divided into Sodium Chromate Tetrahydrate 99 (Na
2(YO
4), alkali or ferric chromate (FeOHCY O
4), iron calcium aluminate (4CaOAL
2O
3Fe
2O
3), Dicalcium Phosphate (Feed Grade) (B-2CaOSlO
2), chromous acid calcium " (a-CaCrO
2) ", calcium carbonate (CaCO
3) etc., water ratio about 15%, the wherein thing phase composite of similar cement greatly, so the chromium slag also has the hydraulicity, suction caking in air.But mainly contain water miscible Sodium Chromate Tetrahydrate 99 (Na in the chromium slag
2CrO
44H
2O), yellow ultramarine (CaCrO
4) be strong oxidizer.
They are to discharge " three wastes " principal pollutant in the chromic salts enterprise production process for chromium-bearing sludges, because its output is big, corrodibility is strong, and factors such as difficult treatment are that chromic salts enterprise is restricted and tie rich important environment reason always.The chromium residue of a large amount of air storages is through rain drop erosion, the sexavalent chrome that underground water leaches in the chromium residue transforms migration, cause serious pollution to local environment and water resources, if do not seek thorough elimination as early as possible, comprehensive utilization processing approach will cause centuries decades even influence more remote to neighboring area and the environmental improvement of territory city.
Salkali waste-solvay soda process of " dangerous register " HW35 is salkali waste and the waste liquid that main soda ash production process is discharged.China exports soda ash year more than 1,000,000 tons now.Because produce the waste residue of a large amount of waste residues, waste liquid, the annual discharging of China with the production process of this method, waste liquid must be nearly 1,000 ten thousand tons.The pH value of alkaline residue and waste liquid, the floating thing content in county; cl content and temperature all do not meet requirement on environmental protection; cause the pollution in various degree of region, alkali factory place, especially make water industry and ecotope be subjected to very grave influence: simultaneously, the waste residue deposition takies a large amount of soils and causes " white sea ".Become and restricted a great problem of soda industry development in the world.Have many factories to permeate the ground because solving " white sea " or waste liquid both at home and abroad, the ocean pollutes and is forced to close.
The alkaline residue chemical ingredients that solvay soda process is discharged is referring to shown in the table-5:
Table-5: the alkaline residue chemical ingredients that certain solvay soda process alkali works discharges
| Test item | Na 2O | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O |
| Detected result | 4.79 | 1.93 | 1.11 | 28.40 | 12.47 | 0.08 |
| Test item | TiO 2 | Cl | SO 3 | SiO 2 | P 2O 5 | Loss on ignition |
| Detected result | 0.07 | 24.19 | 1.13 | 4.75 | 0.05 | 20.48 |
Alkaline residue is because of various places manufacturer raw material and production technology difference, and the chemical ingredients of its alkaline residue is had nothing in common with each other.
The described stablizer of step 3 is 5 Starso (Na
2SiO
3HH
2O n=5), its aqueous solution is alkalescence.Tai-Ace S 150 (Al
2O (SO
4)
318H
2O) and/or potassium aluminium sulfate (AlK (SO
4)
212H
2O), its aqueous solution is acid.The acidic mixed mud that detects is with 5 Starso (Na
2SiO
3HH
2O) used as stabilizers is regulated mixing sludge pH value to 7.5～9, becomes neutral mixing sludge.The alkaline mixing sludge that detects is with Tai-Ace S 150 (Al
2(SO
4)
318H
2O) and/or potassium aluminium sulfate (AlK (SO
4)
212H
2O), used as stabilizers, regulate mixing sludge pH value to 7.5～9, become neutral mixing sludge.
The described solidifying agent of step 5 is the rise building material factory production supply of material of Yin state, Ningbo City, Zhejiang Province.
The described solidifying agent of step 5 is a kind of inorganic coagulation material, and its proterties is as follows:
(1) grey powdered solid
(2) density is 2.70～2.85g/Cm
3
(3) fineness is no more than 4.0% for 80um side tails over
The solidifying agent that the present invention adopts is done gelling material, is because this solidifying agent is a kind of hydraulic cementing materials.Its gelling principle is: solidifying agent directly carries out quick gluing to material granule at normal temperatures, on the phase interface of the basic granules of the material of the active ingredient of solidifying agent infiltration simultaneously, excite the activity of mixing material, utilize the super synergistic effect of the compound production of polycomponent, give the active ingredient dilution dissemination of mixing material, make it to form polycrystalline aggregate, make goods early strong, high-strength.
Because inclined to one side alkali or the strong basicity of industrial residue, incineration disposal residue, MSW flying dust etc., therefore the slant acidity of electroplating sludge etc. utilizes their acid, alkaloid substance to mix neutralization jointly, under the effect of stablizer acid-alkali accommodation, can make the compound trend neutral, strengthen the stability of fragment of brick, building slab.And industrial residue, incineration residue MSW flying dust etc. are also with the intensity of the solid-state increase fragment of brick of particulate state or member.Be convenient to mix and the demoulding.
Because industrial residue, incineration disposal residue, MSW flying dust etc. contain a large amount of SiO
2, Ai
2O
3, CaO main component.Dicalcium Phosphate (Feed Grade) (the C that the phenotype waste residue contains
2S), tricalcium silicate (C
3S) have the hydraulic characteristic of cement, the gelling that awards waste residue provides guarantee.
The gelling principle of active waste residue.Active waste residue is after activation, and it is enclosed in intravitreous silane agent and is gone out by water-soluble, and the performance of its activity begins.But its silicon, aluminium two big compositions itself do not have pectisation.They will produce pectisation, make goods or member produce intensity, also will carry out a series of complex reaction, form silicate and the aluminate of cement composition, and its final gelling just can form and manifest.
Make the silane agent of active waste residue form hydrated silicate and aquation aluminate, a prerequisite reaction conditions must be arranged, that is exactly Ca (OH)
2Existence.Has only Ca (OH)
2Existence, the SiO in the active waste residue
2Could form hydrated calcium silicate with it.As everyone knows, the hydrated product of silicate cement and aluminate cement is only hydrated silicate and aquation aluminate.The hydrated product of active waste residue of the present invention is identical with cement, and its gelling property is also just identical with cement.
Ca (OH)
2Two sources can be arranged, the one, the CaO that active waste residue and solidifying agent contain, the 2nd, from the unslaked lime that adds (CaO), its reaction is as follows.
Active waste residue, solidifying agent aquation form Ca (OH)
2:
3CaO·SiO
2+nH
2O→xCaO·SiO
2·yH
2O+(3-x)Ca(OH)
2 (1-2)
The unslaked lime aquation forms Ca (OH)
2:
CaO+2H
2O→CaO+2H
2O (1-3)
CaO+2H
2O→Ca(OH)
2+2H
2O (1-4)
At Ca (OH)
2Form, and reach after the finite concentration, the silane agent of active waste residue stripping just begins with Ca (OH)
2Reaction generates hydrated calcium silicate and drated calcium aluminate.Its reaction is as follows:
SiO
2(activity)+mCa (OH)
2+ aq → mCaOSiO
2Aq (1-5)
Al
2O
3(activity)+nCa (OH)
2+ aq → nCaOAl
2O
3Aq (1-6)
The resultant hydrated calcium silicate mCaOSiO of above-mentioned two reactions
2Aq and drated calcium aluminate nCaOAl
2O
3Aq is gum material, and is identical with the hydrated product of cement.They can cohere various fragments of brick, building slab material particles to become one, thereby produce intensity.When active waste residue such as slag, slag contain Dicalcium Phosphate (Feed Grade) (C
2S) or tricalcium silicate (C
3S) time because the composition that they and cement heat is expected is identical, so they directly aquation become hydrated silicate and aquation aluminate.Like this, these waste residues are a just many again heavy gelling.Therefore, the gelling of these waste residues is stronger, and product strength is higher, and its hydration reaction is as follows.
The Dicalcium Phosphate (Feed Grade) aquation generates hydrated calcium silicate:
2CaO·SiO
2+H
2O→2CaO·SiO
2·H
2O (1-7)
The tricalcium silicate aquation generates hydrated calcium silicate and calcium hydroxide:
3CaO·SiO
2+2H
2O→2CaO·SiO
2·H
2O+Ca(OH)
2 (1-8)
The tricalcium aluminate aquation generates drated calcium aluminate:
3CaO·Al
2O
3+H
2O→3CaO·Al
2O
3·H
2O (1-9)
The present invention finds: as lime and SiO
2The material mixing that content is high, hydro-thermal is steam-cured or when steam pressing, and excellent gelling in will manifesting produces high intensity.When steam-cured temperature rose to 174.5 ℃, its sclerosis will be accelerated greatly, was hardened to rostone in the short period of time.When adding the pressure of 0.8～1.2MPa, this setting rate can be faster when steam-cured, and the time that forms rostone is shorter.So the contriver utilizes its these sclerosis characteristics, with industrial residue and Hazardous wastes gluing, successful brickmaking.Because this raw material is sufficient especially, grows on trees, and promotes easily.
SiO
2With lime why steam-cured or steam to depress and can produce gelling, the SiO in high silicon or the silica-rich material
2With the Ca (OH) in the lime
2Can carry out hydrothermal synthesis reaction, generate the hydrated product-hydrated calcium silicate CaOSiO with pectisation
2NH
2O, drated calcium aluminate 3CaOAl
2O
3NH
2O and 4CaOAl
2O
3Al
2O
3NH
2O, aquation ca aluminosilicate 3CaOAl
2O
3SiO
2NH
2O etc.These aquation resultants aquation resultant with cement basically are identical.Thereby it can make goods produce very high intensity.
The hydration reaction of cement is normal temperature, and SiO
2Then be steam-cured and steam and press with the reaction of lime.Depress the SiO of non-activity in steam-cured or steaming
2Ca (OH) with lime formation
2Solution has generated the multiple hydrated product of fibrous crystals.The good hydrated calcium silicate of these degree of crystallinity and a spot of holder shellfish mullite gum material cohere other materials and unreacted aggregate, have just formed high-intensity brick.Its principal reaction is as follows:
CaO+H
2O→Ca(OH)
2+15.5kcal (1-10)
Ca(OH)
2+SiO
2(n-1)H
2O→CaO·SiO
2·nH
2O (1-11)
Between above-mentioned resultant, SiO
2Also generate CSH (B), the xonotlite CSH of fiber crystallization, non-fibrous C with the hydro-thermal reaction of lime
2SH (A) or gyrolite C
4S
6H
5Etc. multiple hydrated product, produced comprehensive pectisation, just make the intensity of this brick and performance surpass the sintering clay brick.
The application principle of gypsum.The same with lime, itself has gelling gypsum, but gelling is relatively poor, can not make non-burning brick intensity reach technological standard.It is used for this patent, mainly is the excitation of utilizing active waste residue, assists lime, promotes the reaction of lime and active waste residue, generates more hydrated calcium silicate and drated calcium aluminate.In addition, it can with active waste residue in Al
2O
3Reaction, the ettringite (aquation calcium sulphoaluminate) of generation some amount.Because the hydration rate of ettringite is very fast, so after ettringite generated, the early strength of goods just improved greatly, has overcome the low deficiency of goods early strength, its reaction is as follows:
The beneficial effect that the technology of the present invention produces:
1, the present invention utilizes discarded industrial residue, intrinsic acid, the alkali characteristic of solid dangerous waste, adopts and mixes the method for regulating, and making it mixture becomes neutrality, and trend is stable; Utilize its silicon-dioxide that includes, aluminium sesquioxide and calcium oxide to be main chemical compositions, through chemistry and physical excitation, compound and the usefulness of solidifying agent makes refuse fixed, and fixedly the heavy metal ion such as zh:Cu:N that exist in waste residue and the Hazardous wastes have not soluble end.The redox-potential of control heavy metal generates under the stable common environment and can not leach metallic compound, does not produce radioactive gas.Eliminate pathogeny body, virus, foul gas and organic soil ulmin in waste residue, the Hazardous wastes simultaneously.Make it to reach innoxious, minimizing, stabilization, four standards of resource utilization.
2, the invention of industrial residue, solid dangerous waste recycling patented technology, the Policy Conditions that meet " People's Republic of China's prevention and control of environmental pollution by solid wastes method " the 3rd, the 4th, the 5th, and State Environmental Protection Administration is about the notice spirit of issue " Hazardous wastes pollution prevention technique policy ".Meet State Council about " novel wall reform policy ", adhere to the principle that new wall material should " joint soil, economize ground, sharp useless, environmental protection ".Cater to State Council, each ministries and commissions and local people's governments about every policy and the rules of environment protection, wall reform, building energy conservation.
3, comprehensive regulation industrial and mining enterprises, poisonous in the living environment, harmful waste residue is solid dangerous waste particularly.Changed the cities and towns periphery, river, river, forward position, lake, between crop land, the Ling Ye glass of mountain, waste residue is piled up, the phenomenon that refuse is toppled over.The protection environment has been avoided secondary pollution.Optimize ecotope, be conducive to the health of the person.
4, the comprehensive regulation of industrial residue, solid dangerous waste the time, be converted into comprehensive utilization of resources, provide new resource to society, turn waste into wealth, become the material wealth of society.Save the refuse landfill, piled up land used.Soil-saving brick making is protected farmland, and benefits the nation and the people.Significant social, environment, economic benefit are arranged, and are the industries of a Sustainable development.
5, industrial residue, solid dangerous waste, instead of clay brickmaking, the quality product technical indicator meets and surpasses the autoclaved lime-sand brick national standard (GB17945-1999) that five ministries and commissions' collaborative promotions of country are used.
Product performance: lightweight, high-strength, the insulation, heat insulation, sound-proofing properties is good; The solid brick of making, hollow brick, floor tile, along road stone, specifications wide in variety such as bank protection stone are complete.Be widely used in load-bearing, non-lbearing wall material, square, road, reclaim fields from the sea and water conservancy construction etc.
(4) description of drawings
Fig. 1 is process flow sheet of the present invention
(5) embodiment
Below in conjunction with embodiment, further specify the present invention.The described content of case study on implementation is not limitation of the invention.
Embodiment 1
Present embodiment carries out with following processing step.
(1) mix whipping step: adopt endless belt conveyor with the slag of 50% (weight percent), 35% flyash, 15% electroplating sludge, 15% water under the measure control of material autmatic measuring device and liquid meter measuring device, be added in the SB series twin-shaft mixer, stir 3min, become mixing sludge.
(2) pH value of detection mixing sludge.The pH value 10 that records is alkaline mixing sludge.
(3) mix stone roller and grind step: alkaline mixing sludge is mixed with following (weight percent) component: adopt worm conveyor to carry, alkaline mixing sludge with 86.3%, 0.2% Tai-Ace S 150,12% unslaked lime, 1.5% gypsum powder, 5% water are added to XJ-II series loading planet machine mixing stone roller and grind under the control of material autmatic measuring device and liquid meter measuring device.Stone roller is ground into the neutral compound of pH value 9.
(4) digestion step: neutral compound inputed to carry out material digestion in the continous way slaking silos.It is 50 ℃ that slaking silos keep temperature.Digestion time is 2.5h, becomes the digestion material.
(5) whole whipping step: will digest material and use screw machine, and quantitatively input in the control of material autmatic measuring device in the SB series twin-shaft mixer, and mix stirring with following component, its weight percent is respectively: digestion material 88%, solidifying agent 12%.Regulate digestion material water ratio 18% with an amount of magnetization hot water.Churning time is 3min.It is standby to make base material input reservoir tank.
(6) punch steps: in the base material is framed from the punching press of the quantitative input hydraulic pressure machine of reservoir tank, strike out the solid brick blank.Stamping pressure is according to product design intensity.
(7) maintaining process step: the place temperature was 28 ℃ at that time.Adopt nature precuring method.The solid brick blank is at indoor natural precuring 18h.It is steam-cured to enter autoclave.The goods design strength is 26MPa.194.1 ℃ of autoclave working temperatures, pressure 1.3MPa.Steam the compacting degree: preheating 3.5h under the wet heat condition about 50 ℃ is warmed up to 194.1 ℃ (pressure 1.3MPa), constant temperature (194.1 ℃) 7h, cooling 2.5h (going out the still temperature difference less than 80 ℃) in 2.5h.
Embodiment 2
(1) mixes whipping step: 75% (weight percent) slag, 25% electroplating sludge, 14% water are added in the SB series twin-shaft mixer, become mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) pH value of detection mixing sludge: the pH value 9.5 that records is alkaline mixing sludge.
(3) mixing is ground and is ground step: the alkaline mixing sludge of 86.3% (weight percent), 0.15% potassium aluminium sulfate, 12% unslaked lime, 1.5 gypsum powders, 7% water are added to XJ-II series loading planet machine mixing stone roller grind, grind the neutral compound that is ground into pH value 9.Other technology, parameter are identical with embodiment 1.
(4) digestion step: keeping temperature in the slaking silos is 60 ℃.Digestion time is 2h.Become digestion material, other technology, parameter are identical with embodiment 1.
(5) whole whipping step: with 87% (weight percent) digestion material, 13% solidifying agent, input to mix to stir in the SB series twin-shaft mixer and make the base material.Other technology, parameter are identical with embodiment 1.
(6) punch steps: strike out the solid brick blank.Other technology, parameter are identical with embodiment 1.
(7) maintaining process step: the place temperature was 8 ℃ at that time.Adopt damp and hot precuring method, damp and hot precuring time 48h.Enter the autoclave steam press maintenance.Goods design strength 25MPa.The autoclave working temperature, pressure, it is identical with embodiment 1 to steam the compacting degree.
Embodiment 3
(1) mixing is stirred: slag, 25% slag, 35% electroplating sludge, 15% water of 40% (weight percent) are added to mixing stirring in the SB series twin-shaft mixer, become mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) pH value of detection mixing sludge: the PH9 that records is neutral mixing sludge.
(3) mix to grind and to grind step: neutral mixing sludge, 12.5% unslaked lime, 1.8% gypsum powder, 6% water of 85.7% (weight percent) is added to XJ-II series loads to mix in the planet machine to grind and grind, grind the neutral compound that is ground into pH value 8.Other technology, parameter are identical with embodiment 1.
(4) digestion step: keeping temperature in the slaking silos is 55 ℃.Digestion time is 2.5h, becomes the digestion material.Other technology, parameter are identical with embodiment 1.
(5) whole whipping step: 86% (weight percent) digestion material, 14% solidifying agent are inputed to mixing stirring in the SB series twin-shaft mixer, make the base material.Other technology, parameter are identical with embodiment 1.
(6) punch steps: change framed, the mould of punching press, strike out the hollow brick blank.Other technology, parameter are identical with embodiment 1.
(7) maintaining process step: 2 ℃ of there and then temperature.Adopt damp and hot precuring method.The precuring time is 50h.It is steam-cured to enter autoclave.Goods design strength 18MPa.174.5 ℃ of autoclave working temperatures, pressure 0.8MPa.Steam the compacting degree: 174.5 ℃ (the pressure 0.8MPa) that heat up in the preheating 3h under 50 ℃ of left and right sides conditions, 2.5h, constant temperature (174.5 ℃) 6h, cooling 2h (going out the still temperature difference less than 80 ℃).
Embodiment 4
(1) mixes whipping step: with 35% (weight percent) slag, 20% slag, 45% electroplating sludge, 15% water, be added in the SB series twin-shaft mixer and be mixed into mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) pH value of detection mixing sludge: the pH value 6.5 that records is acidic mixed mud.
(3) mix to grind and to grind step: 86.3% (weight percent) acidic mixed mud, 0.25% 5 Starso, 12% unslaked lime, 1.5% gypsum powder, 7% water are added to XJ-II series load to mix in the planet machine to grind and grind, grind that to be ground into PH be 7.5 neutral compound.Other technology, parameter are identical with embodiment 1.
(4) digestion step: digestion time is 2h, and other technologies, parameter are identical with embodiment 1.
(5) whole whipping step: 85% (weight percent) digestion material, 15% solidifying agent are added to the interior mixing of SB series twin-shaft mixer stir, make the base material.Other technologies, parameter are identical with embodiment 1.
(6) punch steps: strike out the hollow brick blank.Other technology, parameter are identical with embodiment 1.
(7) maintaining process step: the place temperature was 32 ℃ at that time, adopted nature precuring method, precuring time 12h.It is steam-cured to enter autoclave.Goods design strength 14MPa, autoclave working temperature, pressure, it is identical with embodiment 3 to steam the compacting degree.
Embodiment 5
(1) mixes whipping step: 60% (weight percent) phosphorus slag, 40% incineration residue, 16% water are inputed in the SB series twin-shaft mixer, become mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) pH value of detection mixing sludge, the pH value 10 that records is alkaline mixing sludge.
(3) mix to grind and to grind step: 83.5% (weight percent) alkaline sludge, 2.5% Tai-Ace S 150,12% unslaked lime, 2% gypsum powder, 8% water are added to series such as XJ-II and load to mix in the planet machine to grind and grind the neutral compound of one-tenth pH value 9.Other technology, parameter are identical with embodiment 1.
(4) digestion step: its technology, parameter are identical with embodiment 1.
(5) whole whipping step: 86% (weight percent) digestion material, 14% solidifying agent is inputed to the interior mixing of SB series twin-shaft mixer stir, make the base material.Other technology, parameter are identical with embodiment 1.
(6) punch steps: strike out the solid brick blank.Other technology, parameter are identical with embodiment 1.
(7) maintenance step: 6 ℃ of there and then temperature.Adopt damp and hot precuring method.Damp and hot precuring time 54h.It is steam-cured to enter autoclave.Product strength design 26.5MPa.The autoclave working temperature, is steamed compacting degree and example and is executed 1 identical pressure.
Embodiment 6
(1) mixes whipping step: 40% (weight percent) slag, 20% flyash, 40%MSW flying dust, 15% water are added in the SB series twin-shaft mixer mix, become mixing sludge.
(2) pH value of detection mixing sludge, the pH value 10.5 that records is alkaline mixing sludge.
(3) mix stone roller and grind step: the alkaline mixing sludge of 84.55% (weight percent), 0.25% potassium aluminium sulfate, 13% unslaked lime, 2.2 gypsum powders, 8% water are added to the interior stone roller that mixes of XJ-II series loading planet machine grind, become the neutral compound of pH value 9.
(4) digestion step: become the digestion material after the digestion.Technology, parameter are identical with embodiment 1.
(5) whole whipping step: 84% (weight percent) digestion material, 16% solidifying agent are inputed to the interior mixing of SB series twin-shaft mixer stir, make the base material.Other technology, parameter are identical with embodiment 1.
(6) punch steps: strike out the floor tile blank.Other technology, parameter are identical with embodiment 1.
(7) maintaining process step: the place temperature adopted nature precuring method for 27 ℃ at that time.Product design intensity 28.5MPa.Steam press maintenance, temperature, pressure and degree of steaming and other technology, parameter are identical with embodiment 1.
Embodiment 7
(1) mix whipping step: with 60% (weight percent) ore in sand form, 40% contain the chromium refuse, 15% water is added in the SB series twin-shaft mixer, is mixed into mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) pH value of detection mixing sludge: the pH value 9 that records is neutral mixing sludge.
(3) mix stone roller and grind step: the neutral mixing sludge of 85.5% (weight percent), 12.2% unslaked lime, 2% gypsum powder, 10% water are added to XJ-II series load in the planet machine, mix and grind the neutral compound that is ground into pH value 9.Other technology, parameter are identical with embodiment 1.
(4) digestion step: with neutral compound input continous way slaking silos, it is 70 ℃ that slaking silos keep temperature.Digestion time 1.5h.Become the digestion material after the digestion.Other technology, parameter are identical with embodiment 1.
(5) whole whipping step: 84% (weight percent) digestion material, 16% solidifying agent are inputed to SB series twin-shaft mixer mix stirring, make the base material.Other technology, parameter are identical with embodiment 1.
(6) punch steps: strike out the floor tile blank.Other technology, parameter are identical with embodiment 1.
(7) maintaining process step: the place temperature was 34 ℃ at that time, adopted nature precuring method, precuring time 8h.Enter the autoclave steam press maintenance.Goods design strength 30MPa, autoclave working temperature, pressure and steaming compacting degree and other technology, parameter are identical with embodiment 1.
Embodiment 8
(1) mixes whipping step: 35% (weight percent) slag, 20% slag, 10% flyash, 35% alkaline residue, 15% water are added in the SB series twin-shaft mixer mix, become mixing sludge.Other technology, parameter are identical with embodiment 1.
(2) detect the mixing sludge pH value: the pH value 12 that records is alkaline mixing sludge.
(3) mix stone roller and grind step: the alkaline mixing sludge of % (weight percent), 3.5% Tai-Ace S 150,13% unslaked lime, 2.5% gypsum powder, 10% water are added to XJ-II series load in the planet machine, mix and grind the neutral compound that is ground into pH value 9.
(4) digestion step: neutral compound input continous way slaking silos are digested material.Become the digestion material after the digestion.Technology, parameter are identical with embodiment 1.
(5) whole whipping step: with % (weight percent) digestion material, % solidifying agent, input in the SB series twin-shaft mixer, be mixed into the base material.Other technology, parameter are identical with embodiment 1.(6) punch steps: change framed, die stamping and become along road stone blank.Other technology, parameter are identical with embodiment 1.
(6) maintaining process step: the place temperature was 21 ℃ at that time, adopted nature precuring method.Precuring time 24h.Go into autoclave and steam pressure.Product design intensity 30.5MPa.Autoclave working temperature, pressure and steaming compacting degree and other technology, parameter are identical with embodiment 1.
Claims (8)
1. the method for an industrial residue, solid dangerous waste recycling, it is characterized in that: this method comprises following processing step:
(1) mix whipping step: adopt endless belt conveyor with the industrial residue of 40～80% (weight percents), 10～80% solid dangerous waste, 0～20% water under the measure control of material autmatic measuring device and liquid meter measuring device, be added in the SB series twin-shaft mixer, stir 2～5min, become mixing sludge;
(2) detect the pH value step: the mixing sludge of step (1) is carried out the pH value detection;
(3) mix stone roller and grind step; Acid or the alkaline mixing sludge of step (2) is mixed with following (weight percent) component; The employing screw machine is carried, with 10～80% acid or alkaline mixing sludge, 0～5% stablizer, 10～30% unslaked lime (CaO), 0～10% gypsum powder (CaSO
42H
2O), 0～10 water, under the control of material autmatic measuring device and liquid meter measuring device, be added to XJ-II series and load to mix in the planet machine to grind and grind.It is 7.5～9 neutral compound that stone roller is ground into pH value;
(4) digestion step: the neutral compound of step (3) inputed to carry out material digestion in the continous way slaking silos.Keeping temperature in the slaking silos is more than 40 ℃.Digestion time is 1～6n, becomes the digestion material;
(5) whole whipping step: the digestion material of step (4) is quantitatively inputed in the control of material autmatic measuring device in the SB series twin-shaft mixer with screw machine, mix stirring with following component, its weight percent is respectively: digestion material 80～90%, solidifying agent 5～20%.Regulate digestion material water ratio 15～20% with an amount of magnetization hot water.Churning time is 2～7min.It is standby to make base material input reservoir tank;
(6) punch steps: in step (5) base material is framed from the punching press of the quantitative input hydraulic pressure machine of material-storing box, strike out solid brick or building product blank.Change framed, mould, goods blank that can the punching press all size.Hydropress pressure is according to product design intensity;
(7) maintaining process step: (1) precuring: adopt nature precuring method or damp and hot precuring method.(2) steam press maintenance: will use autoclave steam-cured through the goods blank of precuring.Autoclave working temperature and pressure should be according to product design intensity.
2. the method for a kind of industrial waste according to claim 1, solid dangerous waste recycling is characterized in that; Industrial residue in the described step (1) refers to the active waste residue of industrial phenotype and the active waste residue of the latent type of industry.
3. the method for a kind of industrial residue according to claim 2, solid dangerous waste recycling, it is characterized in that: the active waste residue of the described industrial phenotype of claim 2, they are slag, slag, phosphorus slag, red mud, shrend copper ashes, ferroalloy slag, silicon manganese slag.The active waste residue of the latent type of described industry, they are artificial sand, building waste pulverizing slags that flyash (II III level ash), coal gangue burn slag, slag, electric furnace slag, phosphogypsum, carbide slag, pyrite cinder, CHARACTERISTICS OF TAILINGS SAND, foundry sand, quartzose barren rock and tankage pulverizing.
4. according to the method for claim 2 or 3 described a kind of industrial residues, solid dangerous waste recycling, it is characterized in that; The active waste residue of described industrial phenotype and the active waste residue of the latent type of industry, they both can use separately, also can two kinds of two or more collocation use.Separately or the active waste residue of phenotype that uses of collocation and the SiO of the active waste residue of latent type
2, Al
2O
3, CaO chemical ingredients, content is more than 70%.
5. the method for industrial waste according to claim 1, solid dangerous waste recycling, it is characterized in that: the described solid dangerous waste of step (1), they are plating water treatment sludge, incineration disposal residue and MSW flying dust, contain chromium refuse, salkali waste, asbestos refuse.
6. the method for a kind of industrial residue according to claim 1, solid dangerous waste recycling is characterized in that; Described step (2) mixing sludge carries out pH value and detects, and pH value below 7.5 is acidic mixed mud.PH value more than 9 is alkaline mixing sludge.
7. the method for a kind of industrial residue according to claim 1, solid dangerous waste recycling, it is characterized in that: the used stablizer of step (3), they are 5 Starso (Na
2SiO
3HH
2O h=5), Tai-Ace S 150 (Al
2(CSO
4)
318H
2O) and/or potassium aluminium sulfate (AlK (SO
4)
2L2H
2O).
8. the method for a kind of industrial residue according to claim 1, solid dangerous waste recycling, it is characterized by: the described acidic mixed mud of step (3), used stablizer are 5 Starso (Na
2SiO
3HH
2O h=5).The alkalescence mixing sludge, used stablizer is Tai-Ace S 150 (Al
2(SO
4)
318H
2O) and/or potassium aluminium sulfate (AlK (SO
4)
212H
2O).
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| CN101885600A (en) * | 2010-07-21 | 2010-11-17 | 中南大学 | Heavy metal waste slag treatment method and sulfur building material prepared thereby |
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