CN101119943A - Process and apparatus for converting spent potliners into a glass frit, and resulting products - Google Patents
Process and apparatus for converting spent potliners into a glass frit, and resulting products Download PDFInfo
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- CN101119943A CN101119943A CNA2005800481602A CN200580048160A CN101119943A CN 101119943 A CN101119943 A CN 101119943A CN A2005800481602 A CNA2005800481602 A CN A2005800481602A CN 200580048160 A CN200580048160 A CN 200580048160A CN 101119943 A CN101119943 A CN 101119943A
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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 present invention relates to a fire metallurgy method for converting the waste slot liner or other harmful material from the aluminum production industry to the glass clinker clew of amorphous fluorine-bearing sodium aluminosilicate and amorphous fluorine-bearing aluminum calcium silicate and converting to the high-carbon material and the device. The raw materials of waste slot liner, silicon dioxide or siliceous material and calcium oxide are added to the non-burner end of the counterflow rotary burner. The material is heated to destroy the cyanide, the salt fluoride is converted to calcium fluoride and forms a homogeneous liquid material. Then the carbon is physically separated from the material. Afterwards the material is glassed to generate the valuable glass clinker clew and high-carbon material.
Description
Technical field
The present invention relates generally to processing from the manufacturing waste tank lining of aluminium or other harmful material.Especially, the present invention relates to waste tank lining is converted into the pyrometallurgy method and apparatus of glass frit and the product that obtains by this method.
Background technology
In the aluminium production process, aluminum oxide is dissolved in the sodium aluminum fluoride in electrolyzer or electrolyzer, wherein said electrolyzer or electrolyzer are by refractory materials box hat protection and make liner of carbon.Many grooves surpass 100 usually, and arranged in series is to form the electrolytic cell row.Described groove is equipped with mainly by sodium aluminum fluoride (Na
3AlF
6) the fused electrolytic solution formed and in about 930～1000 ℃ of operations down.Other material is joined in the described electrolytic solution to improve operation efficiency or to reduce energy expenditure, for example aluminum oxide, aluminum fluoride, Sodium Fluoride, SODA ASH LIGHT 99.2, Calcium Fluoride (Fluorspan), Quilonum Retard and magnesium oxide.
The thorax or the liner in described pond are made of carbon, and it has the insulation backing and is included in the stainless steel vessel that is called as pot shell (potshell).The carbon part of liner is as negative electrode and hold fused electrolytic solution.Carbon lining is made of the prefabricated carbon piece that links together by carbon paste, and described carbon paste is hydraulically filled out in the seam between the carbon piece.The sidewall of liner forms with carbon paste usually, but can contain prefabricated carbon piece.
In the use of negative electrode and pond liner thereof, carbon and insulating material can be flooded by fluoride salt.Therefore may take place to break or the too inefficacy that causes of protuberance because of liner.When described inefficacy takes place, described pond is removed from production line, and described cathode lining material is removed from pot shell by mechanical excavating equipment.This depleted cathode material is called as waste tank lining (SPL).
Except containing above-mentioned fluoride salt, SPL also contains by the opening of air by pot shell and enters, subsequently the prussiate that is formed by nitrogen and carbon lining reaction.
Waste tank lining by Environmental Protection Agency (EPA) on September 13rd, 1988 (53Fed.Reg.35412) according to 40C.F.R., Part 261, Subpart D classifies harmful waste (K088) as, because it may contain a large amount of hexacyanoferrate title complexs and free cyanide.Therefore, in aluminium industry, need a kind of method that makes waste tank lining toxicide economy, make that the resistates of having handled is not a harmful waste.This is important, reason need to be the scheme of alternative landfill harmful waste, this was confirmed as national policy in 1984 in RCRAHazardous and Solid Waste Amendments (HSWA), and was that expection lacks the harmful waste processing power.
The component of SPL is an alterable height.An analyst coverage is as shown in table 1.The method of treatment S PL should be general, be enough to handle the SPL that when using different groove designs, electrolytic solution composition and insulation to seal (insulation package), produces, and any resistates that is produced should satisfy the expection ultimate value to the EPA-definition of related all components (for example, prussiate, fluorochemical, organism and metal).The SPL component that the environment aspect is worried most is prussiate and soluble fluoride salt.Environment and due care be the existence of the reactive material of water (carbide), it forms in the groove use, and be exposed to water or even airborne moisture in can produce explosion gas (hydrogen, methane and ammonia).
The chemical constitution of table 1. waste tank lining
| C | Al | Ca | Mg | Na | Si | F | Fe | CN | S | |
| Weight % | 10- 50 | 5- 22 | 1- 8 | 0.2- 1 | 7- 20 | 1- 20 | 10- 19 | 0.3- 5 | 0.2- 0.5 | 0.01- 0.3 |
The aluminium industry has realized that the disadvantageous effect of SPL to environment for a long time, and has proposed multiple improvement and/or processing selecting.These selections comprise landfill, as the recirculation of other industry feed, fluidized-bed combustion, sodium aluminum fluoride recovery, thermal hydrolysis, hot thiolysis (pyrosulfolysis) etc., described other industry is iron and steel, cement, aluminium or mineral wool industry for example.Landfill is selection of present available, but will become more and more expensive, may be under an embargo at last, because need the landfill yard of harmful waste.
Some existing treatment process is described below, and it is divided into two types according to incendiary carbon amount in described method.Three kinds of methods of first type if any also are to operate under the condition of small amount of carbon in burning.In these three kinds of methods, carbon remains in the final product.
U.S. patent No.5,164,174 (Reynolds Metals Company) have described and have a kind ofly made the SPL method for detoxification by thermal treatment in the adverse current rotary kiln.Add Wingdale and metal silicate to destroy prussiate by oxidation and soluble fluoride salt to be converted into the mineral of relative insoluble Calcium Fluoride (Fluorspan) and fluoride.Air discharged contains fluorine and prussiate seldom, because low furnace operating temperature (600～870 ℃).Ash and granule materials is removed and be recycled or landfill again.The material of getting rid of is by air cooling and contain carbon.But, because low relatively treatment temp, by NaF to CaF
2Conversion insufficient.
U.S. patent No.4,497,464 (Ogden Environmental Services) have described a kind of method of handling the SPL that ground, cyanide content is reduced to the level of environmental sound.Under the temperature of about 260 ℃～about 760 ℃ (500 ～1400 ), in air or stream of nitrogen gas, burn the SPL that pulverizes.Reduce the level of prussiate, and the carbonaceous material of the major portion of not burning, obtained the final product of rich carbon and fluorine.Since do not add calcium oxide source, so following reaction does not take place:
CaCO
3→CaO+CO
2；
2NaF+CaO → CaF
2+ Na
2O; With
2AlF
3+3CaO→3CaF
2+Al
2O
3。
Therefore, fluoride salt is not converted into stable Calcium Fluoride (Fluorspan).The Ogden discharge is essentially the landfill material.
U.S. patent No.4,993,323 (Tabery etc.) have described a kind of method by come thermolysis SPL by fluidized-bed combustion (FBC) in the mixture of brown coal and Wingdale.Fluoride salt is converted into Calcium Fluoride (Fluorspan).Residual a large amount of carbon in final product.
The following method that is used for treatment S PL causes the burning of a large amount of carbon.
U.S. patent No.4,763,585 (Ogden Environmental Services) have described the method for the SPL that a kind of Powdered inertia agglomeration resistance additive burning of using about 1wt%～about 20wt% ground.Burn SPL down at 1400 ～about 2200 (760 ℃～1204 ℃).Pollution components is incorporated into or is coated in the glass solid slag, and the glass solid slag of gained is described to glass sodium Metal 99.5 (Al) silicate substrate and coats the fluorine resistates.Silicon-dioxide is added in the charging.Adjusting condition washes described hydrogen fluoride with water to produce hydrogen fluoride solution to produce hydrogen fluoride.High temperature of combustion makes that a large amount of carbon are burned.Since do not add calcium oxide source, so following reaction does not take place:
CaCO
3→CaO+CO
2；
2NaF+CaO → CaF
2+ Na
2O; With
2AlF
3+3CaO→3CaF
2+Al
2O
3。
In fact, aluminum fluoride and hydrogen fluoride have been produced.Simultaneously, this method can not be converted into Calcium Fluoride (Fluorspan) with all fluoride salts fully.In fact, a large amount of Sodium Fluorides will evaporate, and only have fluorine to be coated as calcium salt.
U.S. patent No.5,711,018 (Alcoa) have described a kind of use industrial waste treatment facility (IWMF) of combustion gas rotary kiln treatment S PL in the same way.IWMF reclaims fluorochemical and is recycled in the molten bath and collection and recovery glass frit resistates from waste gas.Service temperature is 1150 ℃～1250 ℃, and for avoiding producing fluoride gas, temperature can not be above 1250 ℃.Add solid oxidation and gasification reagent (for example Wingdale) to form CO
2, CO
2Form CO with the C reaction.CO burns on molten bath.Siliceous materials is added in this bath.Fluorochemical is fixed in the frit.Carbon is burned, because it is to the deleterious effect of porousness and leachability and do not wish that it stays in the frit.Adding silicon-dioxide helps fluorochemical is converted into stable form.Because described fluoride salt dynamic performance is poor, thereby is difficult for being converted into Calcium Fluoride (Fluorspan).
U.S. patent No.5,286,274 (Elkem Technology) described a kind of with SPL as filler or as the treatment process of raw material.With the SPL that pulverizes, randomly and SiO
2The source is provided in the airtight electric smelting furnace.SPL fusion under 1300 ℃～1750 ℃ temperature.Oxygenant is provided in the stove with carbonoxide and other oxidable component, for example metal, carbide and nitride.Also calcium oxide source is formed CaF to react with all fluorochemicals that exist
2Contain CaF with formation
2Calcium aluminate or the necessary amount of ca aluminosilicate slag be provided in the smelting furnace.It is liquid that slag is bathed in stove under the temperature, and it is randomly drawn and be cooled to bulk or particulate state with metallographic phase from stove.The burning prussiate, fluoride salt is difficult for being converted into Calcium Fluoride (Fluorspan).
U.S. patent No.5,245,115 (Aluminium Pechiney) have described and have been mixed with mineral additive and (are selected from anhydrous CaSO
4, CaO and composition thereof) the thermal shocking of SPL of grinding handle.Fusion or fusion or not fusion or not the fusion described mineral additive combine with fluorochemicals, with formation CaF
2, the NaF of nepheline, hauyne or similar type, CaF
2, SiO
2, Al
2O
3, CaSO
4, Na
2SO
4Binary, ternary or tetraplex.Fluoride salt is difficult for being converted into Calcium Fluoride (Fluorspan).
U.S. patent No.4,113,832 (Kaiser Aluminum ﹠amp; Chemical Corporation) described be used to handle waste material for example cleaning, the floor of SPL, pipeline and groove cleaning and handle method from the waste alumina of the emission gases of purge drying cleaner.Described waste material is thermal hydrolysis at elevated temperatures.Fluorochemical for example NaF and HF can be from the emission gases that produces by thermal hydrolysis, reclaimed, simultaneously, aluminum oxide and Na can be from the solid residue of thermal hydrolysis, reclaimed
2O perhaps reclaims sodium aluminate if necessary.
U.S. patent No.4,735,784 (Morrison-Knudsen Company Inc.) has described and has handled by the method for nonvolatile substantially solid waste of temperature-sensitive contaminants.At least a portion pollution components (that is fluorine) is decomposed or becomes gas by melt.With the slag cooling, and make residual any pollution mixture be attached to or be coated in the vitreous solid slag.Resistates from the slag making reaction is a vitreous solid sodium Metal 99.5 silicate substrate.Basically all fluorine have all volatilized and have been hunted down as HF.
U.S. patent No.6,074,623 (Vick etc.) have described by gasification technology and have transformed SPL to make the vitreous glass frit of inertia and to comprise the method for the valuable gases of hydrogen fluoride, hydrogen and carbon monoxide.Basically all fluorine have all volatilized and have been hunted down.
U.S. patent Nos.5,164,174 (Reynolds), the described first kind method of 4,497,464 (Ogden) and 4,993,323 (no transferee) are even what relate to is to have the words of carbon also to have only a small amount of burned method.In all examples, carbon remains in the finished product.Therefore, described method can't provide the process that carbon is removed.Similarly, these methods can't provide the product that carbon is removed.
U.S. patent Nos.4,763,585 (Ogden), 5,711,018 (Alcoa), 5,286,274 (Elkem) and 5,245,115 (Aluminum Pechiney) and 4, ensuing method described in 113,832 (Kaiser) relates to the most of carbon of burning and attempt to catch the method for fluorine in final product.Carbon can not recirculation and be difficult to fluoride salt is converted into Calcium Fluoride (Fluorspan) when adopting these methods.
At U.S. patent Nos.4, the method that makes a large amount of fluorin volatilizations and a large amount of carbon of burning has been described in the 3rd last class methods described in 113,832 (Kaiser), 4,735,784 (Morrison-Knudson) and 6,074,623 (no transferee).These patents can't be provided at and catch fluorine and the method for separating carbon by physical unit in the frit effectively.
Therefore, be desirable to provide the method that SPL is converted into glass frit of at least one shortcoming that can eliminate or alleviate prior art.
Summary of the invention
The objective of the invention is to eliminate or alleviate at least one shortcoming of method, device and product formerly.
In first aspect, the invention provides the method that comprises the steps: mix waste tank lining, calcium oxide source and silica source and heating, to destroy prussiate, fluoride salt to be converted into Calcium Fluoride (Fluorspan) and formation is mainly amorphous uniform liquid material; From this material, physically isolate carbon; With this material of vitrifying.
In one embodiment, about 9%～about 19% of whole chargings is aluminium.In one embodiment, heating is carried out with reflux type.In one embodiment, this method mix and heating steps after, comprise that also glass makes step, wherein material being remained on is enough to improve matrix and forms and enough advantageously make carbon from described material under the isolated temperature.In one embodiment, waste tank lining is pulverized to less than 6mm.In one embodiment, make the material vitrifying by quenching.In one embodiment, use the calcium oxide of q.s, according to: CaCO
3+ 2NaF → CaF
2+ Na
2O+CO
2, make CaCO
3Be converted into CaF fully with NaF
2, Na
2O and CO
2In one embodiment, add a certain amount of calcium oxide, make that the CaO and the ratio of vitrifying material are about 0.04～0.10.In one embodiment, add a certain amount of silicon-dioxide, make Na in the vitrifying material
2O/Si
2O
3Ratio be about 0.21～about 0.36.In one embodiment, material is heated to about 800 ℃～about 1200 ℃.In one embodiment, in that being retained under the temperature in the described material, fluorine and carbon heats.In one embodiment, glass is added in the puddle of described material, to increase the cementing property of output and the described vitrifying material of improvement.In one embodiment, after vitrifying, improved grinding is arrived about 4000m
3/ kg～about 8000m
3/ kg.
On the other hand, the invention provides device, comprising: (a) first container is used to heat the mixture of waste tank lining, silica source and calcium oxide source, to destroy prussiate, fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms the uniform liquid material; (b) second container is used for physically separating carbon from described material; (c) the 3rd container is used to make the material vitrifying.In one embodiment, first container is the rotary kiln that is used for the heating of adverse current form.In one embodiment, second container is to be used for that material is remained on to be enough to increase matrix formation and enough advantageously to make carbon make stove from the glass under the isolated temperature of described material.In one embodiment, the 3rd container is a quenching bath.
On the other hand, the invention provides vitrifying material by method for preparing.
On the other hand, the invention provides amorphous solid substrate that is mainly of fluorine calcium aluminosilicate and fluorine sodium aluminium silicate, it is made by waste tank lining, and carbon content is about 5wt%～about 25wt% less than about 1wt% and Calcium Fluoride (Fluorspan) content, has cohesiveness when being ground to particulate.In another embodiment, solid is at least about 95% or amorphous, perhaps amorphous at least about 99.8% at least about 99%.In one embodiment, solid is a particle form.In one embodiment, solid Bu Laiyin value (Blainevalue) is about 2000～8000cm
2/ g.In one embodiment, solid weight is composed as follows: about 5～35% CaF
2, about 30～60% SiO
2, about 5～25% Na
2O, about 10～25% Al
2O
3With less than about 1% carbon.In one embodiment, solid weight is composed as follows: about 10～25% CaF
2, about 35～45% SiO
2, about 10～15% Na
2O, about 18～23% Al
2O
3With less than about 1% carbon.
On the other hand, the invention provides above-mentioned amorphous solid purposes that is mainly, it makes concrete binding agent with alkaline activation agent conduct.
On the other hand, the invention provides and comprise portland cement, the above-mentioned composition that is mainly amorphous solid, fumed silica (silica fume) and slag.In one embodiment, described composition comprise about 30～40% portland cement, about 5～35% be mainly amorphous solid, about 2～8% fumed silica (silica fume) and about 20～30% slag.
On the other hand, the invention provides the above-mentioned purposes that is mainly amorphous solid as the portland cement substitute, it measures about 20wt%～about 30wt%.
On the other hand, the invention provides the above-mentioned purposes of amorphous solid in cement that be mainly, its amount is higher than about 90%.
On the other hand, the invention provides the above-mentioned purposes that is mainly amorphous solid as hydraulic binder.
In conjunction with the accompanying drawings to the description of specific embodiments of the present invention, others of the present invention and characteristics are conspicuous for those of ordinary skills based on following.
Description of drawings
To only describe embodiment of the present invention with reference to the accompanying drawings now by embodiment, wherein:
Fig. 1 is schematic representation of apparatus according to embodiments of the present invention;
Fig. 2 is the skeleton diagram of method according to embodiments of the present invention;
Fig. 3 represents the schema of method according to embodiments of the present invention;
Fig. 4 is the synoptic diagram of the gas circuit of method according to embodiments of the present invention;
Fig. 5 is the synoptic diagram of the solid path of method according to embodiments of the present invention;
Fig. 6 is the synoptic diagram in the water route of method according to embodiments of the present invention;
Fig. 7 is the diffractogram of product according to embodiments of the present invention;
Fig. 8 is the figure of the concrete chloride ion permeability of several blending of expression, and wherein part kind concrete contains product according to embodiments of the present invention; With
Fig. 9 is the figure of several concrete rate of expansion of expression, and wherein part kind concrete contains product according to embodiments of the present invention.
Embodiment
The present invention provides the glass frit that waste tank lining (SPL) or other harmful material from aluminium manufacturing industry are converted into commercially available non-crystalline state fluorine sodium aluminium silicate and fluorine calcium aluminosilicate usually, and (for example, its trade mark is CAlSiFrit at present
) and the high-carbon material (for example, its trade mark is CAlSiCoke at present
) the method and apparatus of pyrometallurgy.The non-burner end that waste tank lining, calcium oxide source and silicate source material is added the adverse current rotary kiln.Heating raw is to destroy prussiate, fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms uniform liquid material.Then from the placed in-line bed furnace of rotary kiln described material in physically isolate carbon, the described material of vitrifying then.Rotary kiln all links to each other with flare system with bed furnace.
Term " waste tank lining " is known in this area.The word that " gives up " is not intended to speech " waste tank lining " is restricted to the slot liner of using up fully, because manufacturers can change the time of slot liner according to different standard decisions.In some cases, according to the operation of factory, changing slot liner to slot liner before work-ing life far away.Can handle other harmful material according to present method, especially contain harmful material of aluminium, calcium or silicon, for example from the catalyzer of petroleum refining, polycyclic aromatic hydrocarbons, contaminated refractory materials, the mud of purifying waste water with from the carbon anode of aluminium smelting furnace.
Describe according to device of the present invention now with reference to Fig. 1.SPL, the energy and additive are joined the non-burner end (that is the right-hand side of Fig. 1) of long body rotary kiln (101).Material arrives glass by described stove and makes stove (103) and quenching bath (105).Gas and water treatment system combine with this device, as detailed below.
For the general description of present method, with reference to figure 2, SPL (201), the energy (203) and additive (205) are added in the long body rotary kiln (207), heat.Handle gas and gas partly is recycled in the stove (207) by gas treating system (208), the gas of having handled is got rid of by chimney (211).In the exit of stove, material falls into glass and makes stove (209), isolates high-carbon material (217) in this stove, and leftover materials forward quenching bath (213) to, is glassed to frit (218) in quenching bath.A part of water from quenching bath (213) is fed to gas treating system (208), and surplus partly is fed to cooling loop (214) and water treatment system (215), is cooled therein and turns back to quenching bath (213).Because this process consume water, thereby add make up water (216).
Fig. 3 is a process flow sheet.Mix the charging and the heating (301) that comprise SPL and additive, to form liquid material.From described material (303), physically separate carbon.Make described material vitrifying to produce glass powder (305).Between step (301) and (303), described material can be kept at high temperature forming (302) to increase matrix.Below this technology will be described in more detail.
A) pulverizing of mixture and preparation.(i) SPL is crushed to the yardstick of average 6mm and sampling continuously in storage process.In integrated system, in silo filler (silo filling) process, take a sample, make computer have the material of analyzing free corresponding information.As an example, can use eight silos to be fed to SPL in the stove simultaneously with homogenizing suitably.Because the reactivity that material and water in air are divided, for a large amount of storings that reclaim, particularly design comprises blast inlet and filtration airy silo is preferred under indoor storage situation.(ii) the SPL of Fen Suiing is isolated, and waits to be analyzed.(iii) after obtaining the chemical constitution data of SPL, during the corresponding charging of SPL, additive and reagent are joined in the analyte.Determine the amount of additive and reagent by software program, so that consistent charging to be provided.The material that will contain aluminum oxide for example recycle stock is added among the SPL, so that total Al content is about 9～19%, preferred 13.5% of combined feed total feed.Scheme will be pulverized behind the SPL mixing formation prescription more as an alternative.Add enough calcium (CaCO for example
3, Wingdale, calcium oxide (or unslaked lime), white lime or rhombspar and calcic refuse) to realize following simplification reaction:
CaCO
3+2NaF→CaF
2+Na
2O+CO
2
Add excessive calcium, the ratio that surpasses the CaO/ glass frit of above-mentioned stoichiometric reaction amount is about 0.02～0.12, preferred about 0.07.According to the sodium of SPL, add the silicon-dioxide of capacity, make final Na in the glass frit
2O/Si
2O
3Ratio be about 0.16～0.36, be preferably about 0.26.
B) stove charging.Stove is preferably long body rotary kiln (LBRF) or kiln.Material is from upstream to the downstream and passes through different heat and physical stage forward.Transmitter and/or chute that through-rate is controlled are fed to raw material in the stove.
C) operation of long body rotary kiln (LBRF).(i) diameter of LBRF is 3m, and length is 40m.Should be appreciated that though may describe or show specific dimensions or shape in whole specification sheets, this only is illustrative and nonrestrictive.Along its whole length the infrared temperature detector is set,, thereby measures the interior temperature variation of stove with the outside temperature of measurement stove.In case establish control, just can monitor the cold junction temperature of process gas (process gas) and the temperature of outlet material fully, (ii) along with material moves in stove, it begins little by little to be heated from envrionment temperature.Thermal source makes this process adverse current in the downstream.Fig. 1 represents each stage of material process.Section 1 (1001) enters cold section of stove for material.Section 2 (1002) for material be heated to 800～1200 ℃ and take place chemical reaction section.In section 3 (1003), solid materials melts lentamente, proceeds chemical reaction simultaneously.In section 4 (1004), material is liquid and chemistry binding (chemical liaison) takes place.Section 5 (1005) expressions second glass is made stove, carries out the separation of carbon at this.Described second glass is made stove should make carbon separate from matrix effectively.Section 6 (1006) expression quenching baths.(iii) elevated temperature helps destroying some existing chemical bond and forms the key that determines new component.This causes that destroyed and fluorochemical experience sodium key changes to the calcium key and is hunted down prussiate by oxidation.Principal reaction is as follows:
2CN+2O
2→2CO
2+N
2
CaCO
3→CaO+CO
2
2NaF+CaO→CaF
2+Na
2O
2AlF
3+3CaO→3CaF
2+Al
2O
3
(iv) anisotropically form by solid materials, little by little become liquid composition equably at the material of LBRF ingress.In section 4 (1004), form that matrix is concurrent gives birth to two reactions of row:
CaF
2+SiO
2→Na
2O+Al
2O
3
C+O
2→CO
2
D) vitrifying of silicon matrix.(i) in the exit of LBRF, now be that amorphous material falls into the second non-rotating stove or glass is made stove (GFF), with the prolongation residence time at high temperature, thereby guarantee being completed into of fluorine calcium aluminosilicate and fluorine sodium aluminium silicate composite interstitial substance.GFF also makes carbon generation gravity separation, and by sifting out or blow out carbon, obtains containing the matrix of minute quantity carbon.Recovery floats over the carbon on the matrix, rather than burns.This high-carbon material analyzed obtain the same high carbon content with the most of metallurgical cokes that on market, find.Analyze from chemistry, it is made up of the pyrometallurgy coke that contains greater than 80% carbon.In being less than 20% ash, Calcium Fluoride (Fluorspan) accounts for 2～4%, and this level has remarkable advantage for fluidisation and the eutectic point that reduces clinker and metallurgical slag.In this process, the recovery of residual carbon increases the overall coordination effect and the same greenhouse gases effect that reduces used waste tank lining metric ton number of recirculation waste tank lining.(iii) the glass precursor solution that will draw thus is dipped in the water apace, promptly to reduce the non-crystalline state characteristic of one of temperature and its essential property of maintenance.(iv) dry and pulverize the glass frit of gained.Preferably glass frit is crushed to the Bu Laiyin value and is about 2000～8000cm
2/ g is preferably about 4000～6000cm
2/ g.The glass frit of matrix form is by CaF
2(5～35%, perhaps preferred 10～25%), SiO
2(30～60%, perhaps preferred 35～45%), Na
2O (5～2, perhaps preferred 10～15%) and Al
2O
3(10～25%) are formed.Also there are more a spot of CaO (3～12%) and Fe
2O
3(1～3%).Exist and be less than 1% carbon.Glass frit is about 1.4 or 1.55 with the ratio of SPL.
E) processing of gas.Fig. 4 represents gas return path.(i) in order to be captured in all gas that produces in the glass frit manufacturing processed, connect LBRF (403) and GFF (401) by megathermal movable head.The burner of LBRF is shown in (402), and the burner of GFF is shown in (412).This has guaranteed closed system, and described system makes all incendiary gases and generation under negative pressure gas (decomposition of the carbonate and the hexacyanoferrate etc.) enters into after burner and purification system (404) before being discharged into chimney (410).(ii) first class purification carries out in the surge chamber (403a) of stove, by the vertical outlet arrival high temperature cyclone separator (not shown) of gas.This has been avoided carrying secretly in a large number of downstream dust.Cyclonic separator is dispensable.Dust one is separated from flowing gas, just is fed to (following with reference to figure 5) among the LBRF again by the feeding-in solid body loop.(iii) the temperature with the after burner system is elevated to about 775～950 ℃, preferred 875 ℃ with burning CO with remove for example polycyclic aromatic hydrocarbons of obnoxious flavour pollutent.(iv) then gas cooling is arrived and filter bag (407) consistent temperature.This step also in and the sour gas that in dry type reactor (406), will further be removed.(v) by injecting calcium hydroxide, dry type reactor (406) is removed HF and other acid, and described HF and other acid may be found in the gas that after burner (411) produces.Have fluorine if detection system is shown in the gas of chimney, then dry type reactor (406) automatically increases the injection of calcium hydroxide, with the quality of the discharge of guaranteeing to enter into atmosphere.(vi) filter bag (407) catches the solid dust of self-drying type reactor (406).On filter pad (filtrating sleeves), exist sufficient filter cake to help guaranteeing that acidic molecular is by Ca (OH)
2Absorb, and therefore play the effect of similar dry type reactor (406).For GFF (401), there is another burner (412).Locate gas-firing and/or other inflammable substance in (413).Locate Sweet natural gas is carried out continuously measured in (414).Other liquid or solid inflammable substance can be used for the kiln burner.At the preferred Sweet natural gas in after burner place, to guarantee the perfect combustion of all the components, this is the purpose of after burner.
F) detection of atmospheric emission.Fig. 4 represents gas return path.(i) after the filtration, gas enters into chimney (410).Locate to measure continuously atmospheric emission: HF, CO, CO at atmospheric analysis and sampling spot (409)
2, O
2, SO
2, NO
x, and opaqueness.
G) processing of dust and returns.Fig. 5 represents the solid loop.(i) will send back in the feeding-in solid body from all dust of gas processing and the stove that reinjects in.For example useless kiln refractory materials such as charging chip (feed debris), quench water processing mud (quench-water treatment mud) also is recycled to this process.SPL is from SPL container (501), through hopper (502) and transmitter (503), though transmitter is dispensable.Pulverize SPL and make its homogenizing enter in the storehouse of silo and be selectable and be preferred.Additive silo (504) is preserved additive.Prescription hopper (505) and batch hopper (506) are used for charging.Be fed to again in the batch hopper (406) with the recycled matter (508) of charging chip (507), afterfire and adjusting with from the recycled matter (509) of filter bag.LBRF (510), LBRF burner (511), GFF (512), high-carbon material container (513), glass frit quenching bath (514), automatic glass frit sampler (515) and glass frit (516) also are shown.
H) water treatment.Fig. 5 represents water loop.(i) lime is added in the treating water to prevent its acidifying.Then described water is cooled off before getting back to quenching bath being recycled.(ii) a part of water flows to the adjusting tower of after burner.Realize water cooling by evaporation.Generally speaking, therefore this process consume water does not have waste water to discharge.With reference to figure 6, show that glass frit (609) is from quenching bath (601).Water from quenching bath (601) flows through storage pool (603) and pump pond (604), so a part is added into afterfire and regulates tower (605), and remaining flows to cold water treatment pond (608), and water evaporates (606) from this cold water treatment pond (608).The water (607) that replenishes is added in the pond (608).In water collecting basin (602), collect waste water and use water collecting basin pump (610) that described waste water is pumped into storage pool (603).Use pond pump (611) that water is pumped into quenching bath (601).
Temperature curve in the kiln
The material temperature of feed end is about envrionment temperature, is 950～1250 ℃ and is preferably 1050～1125 ℃ at exit end.Utilize the state of raw material and the liquidus temperature of raw material, the temperature that calculates apart from 10～12 meters of burner end of stove is 860 ℃.At 1 meter of distance stove, measuring temperature is 1125～1150 ℃.Can control this temperature by the fuel quantity of torch before increasing or reducing.Behind the position and state of the anchor ring at about 10～12 meters of viewing distance burner end, comprise flame pattern from axially changing to the radial additive correction.
The burner end of kiln (outlet of stove) gas temperature is 1450 ℃ and measures the gas temperature and the flow of the feed end of stove.With respect to inlet amount, whether these observed value indicative curves raise or reduce.This confirms the direction that the trend indication process of described shell temperature is carried out by the shell temperature of measuring on about 20 partial continuous ground.The reading of these shell temperature is subjected to influences such as outside temperature, wind, rain, is useful relatively therefore, represents a kind of trend but not absolute value.The reading of described shell temperature also is subjected to the influence of the thickness and the state of refractory lining, and the thickness of described refractory lining is owing to the thickness of the furnace accretion that exists increases.As mentioned above, be useful along the measurement of shell, but not necessarily.
If do not control curve, then the furnace accretion in the kiln will reach the point of charging more apace.In order to remove these furnace accretions, out of service, enter in the stove, physically remove furnace accretion with pneumatic hammer.Verified radially CO
2Air blast, axially gunslinging and overheated himself to removing/control the mode that furnace accretion is a relative nullity.
Kinetics
Counter-current furnace helps the preheating of charging and the cooling of gas.The energy input that is positioned at ventilation installation (408) (see figure 4) before the blowdown stack and main burner by adjusting is controlled the temperature of kiln.
By the LBRF (long body rotary kiln) that uses adverse current to be provided with, along with described raw material is moved down into the hot-zone along kiln, the operator can be suitably, dynamically with the temperature of the relative raw material that raises lentamente.The close contact between different material is guaranteed in the rotation of stove.In the erosion action of a kind of component to another kind of component, rotation also helps the friction of different components.Can carry out necessary reaction with catalysis and successive mode then.
Guarantee the most of volatilization NaF of release and Na of generation of being not intended to by the LBRF that uses the adverse current setting
2O and HF can be by LBRF the cold gas outlet in LBRF condensation and since charging the rubbing effect of wall is brought back in the production materials flow.
Thermokinetics simulation shows and is necessary to minimize H in the stove
2The O quantity of steam, to stop following reaction:
2NaF+H
2O→Na
2O+2HF
Simulation also shows the temperature that is necessary at last to determine this process less than 1200 ℃, with the vapour pressure that reduces NaF with therefore reduce the HF that forms owing to water vapour that natural gas burning was produced.
CH
4+O
2→CO
2+2H
2O
Method of the present invention is utilized these thermokinetics characteristics.Therefore, thus method of the present invention is different from and heats other method that SPL stimulates HF to form apace.
Raw material is 1.5～2.5 hours by the common time of LBRF.
Additional feed material
In one embodiment, use output and the improvement concrete character of additional feed material to improve kiln.Adverse current LBRF has its cold-zone at feed zone (epimere).Raw material is added in the just in time hot-zone in fusion pool in the hypomere of kiln.With 60 feet per seconds this raw material is injected in the kiln, in kiln, to reach 4～6 meters.Then, the raw material that is added have fusion and partly or wholly with the glass matrix blended time.Expection per hour can add high extremely about 7 tons raw material by this way, has therefore greatly increased the quantum of output of kiln.
Inject and also will arrive the hot-zone of kiln, because the raw material that is injected into is broken glass (glass cullet), if at cold epimere described cullet is gone in the stove, then it will influence the fusion (and chemical reaction) of prescription unfriendly.At present preferred glass cullet, but other material can be used.
Structure between the different components of these additives change glass matrixs links, and it influences the reactivity and the consequent glass cementation characteristic of the amorphous glass of manufacturing conversely.The glass frit of reduction recently that reduces Ca and Al and glass frit makes that to vitriol and carbonate erosive susceptibility the concrete of being made by glass frit is more durable.The product that these additives produce provides some in fact to bring concrete performance by silica flour.
Glass frit can at high temperature be made concrete, and does not produce the reaction generation of deleterious ettringite.High temperature shortens the required consolidation time of concrete, therefore increases the turnover ability of pre-control equipment.Use activator that glass frit is converted into and be used to make robust concrete high-performance adhesive (for example, present commodity CAlSiBinderHP by name
).
Mass balance
In the process of 1000 tonnes of waste tank linings of recirculation, as follows to the research of this method mass balance: the fluorine mass balance be 99.26% (the fluorine loss that causes by airborne release only account for the total mass of the fluorine of slot liner form charging 0.003%), CO
2Mass balance is 99.02% (perhaps 100%, consider the permissible error of various surveying instruments), and the solid masses balance is 99.8% (perhaps 100%, consider the permissible error of various surveying instruments).The fluorine mass balance confirms not loss somewhere of fluorine in the method.Measurement is 324.99 ± 2.03 tonnes as the amount of the carbon of slot liner charging, the carbon of surveying in glass frit and high-carbon material is respectively 126.30 ± 0.51 and the 102.1248.17 metric ton, show in the process the stove internal consumption and in chimney the carbon amount with the carbon dioxide quilt be 96.57 ± 8.43 tonnes.Slot liner per ton only produces 0.84 ton of CO
2, to compare with 1.19 tons of another kind of currently known methods, present method is favourable.
Glass frit
Glass frit is for forming the non-crystalline state siliceous materials of fluorine calcium aluminosilicate and fluorine sodium aluminium silicate matrix.This homogeneous solid materials has high reaction potentiality and show fabulous cementing property when being ground to particulate.It is particulate, for example 410m that hard-tempered glass frit is ground
2The powder of/kg.Fig. 7 is the X-ray diffraction analysis of glass frit, shows the non-crystalline state character of glass frit.Though need 95% non-crystalline state character, at least 98% is preferred, and at least 99% is preferred.The chemical constitution of the glass frit that a kind of particular measurement method of table 3 expression use records.Value shown under " standard " hurdle is a ultimate value, surpasses its described material and just is considered to " harmful material ".TCLP is standard operation, is defined as the method for using acidic medium to analyze lixiviation.
| Parameter | Standard | The result |
| Total analysis | ||
| Al，％ | 12.0 | |
| Ca，％ | 12.1 | |
| Mg，％ | 0.5 | |
| Si，％ | 15.4 | |
| Fe，％ | 1.6 | |
| K，％ | 1.55 | |
| Total F, % | 6.2 | |
| Na，％ | 10.2 | |
| Leaching TCLP | ||
| As | ＜5mg/l | ＜0.01 |
| Ba | ＜100mg/l | 0.38 |
| B | ＜500mg/l | 0.09 |
| Cd | ＜0.5mg/l | 0.34 |
| Cr | ＜5.0mg/l | 0.02 |
| Hg | ＜0.1mg/l | ＜0.0004 |
| Pb | ＜5.0mg/l | 3.3 |
| Se | ＜1.0mg/l | ＜0.01 |
| U | ＜2.0mg/l | ＜0.005 |
| Nitrate+nitrite | ＜1000mg/l | ＜0.02 |
| Fluorochemical | ＜150mg/l | 11.9 |
| Nitrite | ＜100mg/l | ＜0.02 |
Glass frit is as viscosity additives and hydraulic binder.When being used as cement intensifier, the report of being made by University of Sherbrooke has proved that glass frit improves the concrete flowability of blending.This rheological property reduces the water and the ratio (W/B) of binding agent.Except the demand (especially in water reducer and high efficiency water reducing agent) that reduces the chemical mixture consumption, the rheological property of this improvement reduces binder content, but does not sacrifice Concrete Construction or physical properties.Glass frit is for improving the chloride ion permeability reductive agent of concrete wearing quality.Fig. 8 represents the result of chloride permeability property testing, described test be under 23 ± 2 ℃ of temperature, water and binding agent carry out according to ASTM C1202 standard after being to solidify 91 days among the RH 100% at 0.35 o'clock than (W/B).The following qualification of the cement of Fig. 8: contrast is 100% portland cement; Binary is 75% portland cement and 25% blast-furnace slag; Binary CF is 75% portland cement and 25% glass frit; Ternary is 75% portland cement, 20% glass frit and 5% silica flour; Quaternary/FA is 50% portland cement, 25% glass frit, 5% silica flour and 20% flying dust; Quaternary/slag is 40% portland cement, 25% glass frit, 5% silica flour and 30% slag.
Fig. 8 shows that when using 25% glass frit as the substitute of portland cement concrete surpasses 50% to the permeability reduction of chlorion.Present preferred 20%～30%.Fig. 8 show the quaternary mixture that contains glass frit cause rate of permeation drop to the cement of making by 100% Portland type 10 the contrast concrete horizontal 1/15
ThConcrete anti-chlorine ion erosional competency is one of most important factor of considering when determining its wearing quality.This just glass frit as the additive part of preponderating.Because its discontinuous pore network has been guaranteed the performance of salt tolerant, acid and water erosion preferably.
Fig. 9 represents the rate of expansion that in the RH 100% under 38 ℃ the temperature concrete column that solidify to surpass 75 * 75 * 300mm in 2 years recorded according to CSA A23.2-14A standard.Replace 25% cement to reduce rate of expansion with glass frit.Stdn was subsequently solidified 853 days, and using the rate of expansion that writes down in the concrete of 100% portland cement is 0.23%; And use the concrete of the cement that contains 25% glass frit is 0.13%.In order to be evaluated at the validity of material in the control alkali-aggregate reaction (alkali-aggregate reaction), the concrete rate of expansion that contains additive after the chapter 6 regulation of CSA standard A 23.2-28A was solidified through 2 years is 0.04% ultimate value.Analysis to figure is reached a conclusion: though glass frit does not meet standard, its rate of expansion is still much smaller than the rate of expansion that is caused by commercially available Portland 10 type cement.Yet although glass frit contains a large amount of alkali, when when being higher than 90% concentration and using, it meets CAS standard A 23, the regulation of the chapter 6 of 2-28A.
Has strong adhesive capacity for amorphous glass frit as cement more than 99.8%.When being crushed to 4000 Bu Laiyin and when combining with the alkaline activation agent with hydration, glass frit becomes effective hydraulic binder, can be used in RPC type concrete.Shown in U.S. laboratory F.L.Smidth, glass frit is crushed to the required energy of 4000 Bu Laiyin is less than brick slag or the required energy of slag.
When using glass frit, concrete soundness and other mechanical property have been improved.So far, all tests of being undertaken by University of Sherbrooke and St.Lawrence Cement have all confirmed this point.More particularly, as wearing quality, the concrete ultimate compression strength of blending, tensile strength and flexural strength have been improved.By replacing used portland cement in the conventional concrete preparation as main wearing quality reagent (principle durability agent) with 20% glass frit, not only improve ultimate compression strength, tensile strength and flexural strength, but also greatly reduced rate of permeation.Though need more a spot of rheological improving agent, its workability has been improved.
The whiteness (paleness) that quilt grinds to the glass frit of particulate is another characteristic.When the aesthetic property of finished product is counted as composition of its quality and wearing quality, like this especially.Glass frit also shows the potentiality as reactive Powdered concrete formulation composition.
This glass frit reduces greenhouse gas emission (GHG).During the substitute of the brick slag in being used as concrete preparation, its generation is equivalent to the effect of the substituted portland cement of 450kgs/mt.When being added to glass cullet in the silica matrix, this GHG effect reaches the substituted portland cement of 650kgs/mt.Therefore in the framework of Sustainable development, it is more eco-friendly and valuable material.On the level of environment and Sustainable development, it is useful especially that glass frit is added in the cement.It by harmful waste is converted into can be commercially available product eliminates the environmental hazard of aluminium smelting furnace.To no longer need the landfill waste tank lining, this is the main Significance for Environment of this method.By using method for recycling cleaning, that resistates is few that residual harmful material is recovered as commodity, there is the important social ecological significance.
The high-carbon material
Another product of glass frit technology is that ((for example, its trade mark is CAlSiCoke at present for high-carbon material or coke
).The carbon content of high-carbon material is the same high with the most of pyrometallurgy coke that find on market.Contained little metal oxide compound gives material extra metallurgical performance, and this is that cement and metallurgical industry are desirable.The main user of high-carbon material can be for needing coke that energy is provided or as the cement and the steelmaker of the means of reduced oxide and recarbonize iron and steel.
The chemical constitution of table 4 expression high-carbon material.
| Parameter | Unit | The result |
| Carbon | ％ | 80.1 |
| Sulphur | ％ | ＜0.1 |
| Total Ca | ％ | 1.5 |
| Total Cd | ％ | ＜0.01 |
| Total P | mg/kg | 290 |
| Total CN | mg/kg | 1.3 |
| Total fluorine | ％ | 2.9 |
| Total Pb | ％ | 0.01 |
| Total Fe | ％ | 0.4 |
| Total Mg | ％ | 0.05 |
| Total Na | ％ | 3.4 |
| Total Si | ％ | 1.5 |
| Total Al | ％ | 3.3 |
| Leaching TCLP | ||
| As | mg/l | ＜0.1 |
| B | mg/l | 1.2 |
| Ba | mg/l | ＜0.01 |
| Cd | mg/l | 0.01 |
| Cr | mg/l | 0.04 |
| Hg | mg/l | ＜0.001 |
| F | mg/l | 74.6 |
| Pb | mg/l | ＜0.02 |
| Se | mg/l | ＜0.1 |
Above-mentioned embodiment of the present invention only is embodiment.For particular, those skilled in the art can replace, revise and change, and do not deviate from scope of the present invention, and this scope only is subjected to the qualification in these appended claims.
Claims (according to the modification of the 19th of treaty)
Statement according to the modification of PCT19 bar
According to the 19 regulation of Patent Cooperation Treaty, present patent application is carried out following modification: replace original right requirement book 1-32 item with the new claim the 1-32 item of submitting to.
1. a method comprises the steps:
Mix waste tank lining, calcium oxide source and silica source and heating, to destroy prussiate, fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms to be generally even amorphous liquid material;
From described material, physically isolate carbon; With
The described material of vitrifying.
2. the described method of claim 1, wherein all about 9wt%～about 19wt% of chargings is an aluminium.
3. the described method of claim 1, wherein said heating is carried out with reflux type.
4. the described method of claim 1 after described mixing and heating steps, comprises that also glass makes step, and wherein described material being remained on is enough to improve matrix and forms and enough advantageously make carbon from described material under the isolated temperature.
5. the described method of claim 1, wherein said waste tank lining is crushed to less than 6mm.
6. the described method of claim 1 is wherein by the described material of toughened glassization.
7. the described method of claim 1 is wherein used the calcium oxide of q.s, makes CaCO
3Be converted into CaF with NaF fully according to following formula
2, Na
2O and CO
2:
CaCO
3+2NaF→CaF
2+Na
2O+CO
2。
8. the described method of claim 1 wherein adds a certain amount of calcium oxide, makes that the weight ratio of CaO and vitrifying material is about 0.04～about 0.10.
9. the described method of claim 1 wherein adds a certain amount of silicon-dioxide, makes Na in the vitrifying material
2O/SiO
2Weight ratio be about 0.21～about 0.36.
10. the described method of claim 1 wherein is heated to described material about 800 ℃～about 1200 ℃.
11. the described method of claim 1, wherein said heating are carried out in that fluorine and carbon are retained under the temperature in the described material.
12. the described method of claim 1 wherein is added to glass in the puddle of described material, to increase the cementing property of output and the described vitrifying material of improvement.
13. the described method of claim 1 wherein after vitrifying, arrives about 4000m with described improved grinding
3/ kg～about 8000m
3/ kg.
14. a device, it comprises: (a) first container is used to heat the mixture of waste tank lining, silica source and calcium oxide source, to destroy prussiate, fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms the uniform liquid material; (b) second container is used for physically separating carbon from described material; (c) the 3rd container is used to make described material vitrifying.
15. the described device of claim 14, wherein said first container are the rotary kiln that is used for the heating of adverse current form.
16. the described device of claim 14, wherein said second container are to be used for that described material is remained on to be enough to increase matrix formation and enough advantageously to make carbon make stove from the glass under the isolated temperature of described material.
17. the described device of claim 14, wherein said the 3rd container is a quenching bath.
18. vitrifying material by the described method preparation of claim 1.
19. fluorine calcium aluminosilicate and fluorine sodium aluminium silicate be mainly amorphous solid substrate, it is made by waste tank lining, carbon content is about 5wt%～about 35wt% less than about 1wt% and Calcium Fluoride (Fluorspan) content, has cohesiveness when being ground to particulate.
20. claim 19 is described to be mainly amorphous solid, it is 95% amorphous that wherein said solid is at least about.
21. claim 19 is described to be mainly amorphous solid, it is 99% amorphous that wherein said solid is at least about.
22. claim 19 is described to be mainly amorphous solid, it is 99.8% amorphous that wherein said solid is at least about.
Be mainly amorphous solid 23. claim 19 is described, wherein said solid is a particle form.
Be mainly amorphous solid 24. claim 19 is described, wherein said solid Bu Laiyin value is about 2000～8000cm
2/ g.
Be mainly amorphous solid 25. claim 19 is described, its weight is composed as follows: about 5～35% CaF
2, about 30～60% SiO
2, about 5～25% Na
2O, about 10～25% Al
2O
3With less than about 1% carbon.
Be mainly amorphous solid 26. claim 19 is described, its weight is composed as follows: about 10～25% CaF
2, about 35～45% SiO
2, about 10～15% Na
2O, about 18～23% Al
2O
3With less than about 1% carbon.
27. claim 19 is described to be mainly amorphous solid purposes, wherein said be mainly amorphous solid with the alkaline activation agent as making concrete binding agent.
28. a composition, it comprises portland cement, described amorphous solid, fumed silica (silica fume) and the slag of being mainly of claim 19.
29. the described composition of claim 28, it comprises the fumed silica (silica fume) of the amorphous solid of being mainly of the portland cement of about 30～40wt%, about 15～35wt%, about 2～8wt% and the slag of about 20～30wt%.
30. the described purposes that is mainly amorphous solid as the portland cement substitute of claim 19, it measures about 20wt%～about 30wt%.
31. the described purposes of amorphous solid in cement that be mainly of claim 19, its amount is higher than about 90wt%.
32. the described purposes that is mainly amorphous solid as hydraulic binder of claim 19.
Claims (32)
1. a method comprises the steps:
Mix waste tank lining, calcium oxide source and silica source and heating, with destroy prussiate,
Fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms be generally even amorphous liquid material;
From described material, physically isolate carbon; With
The described material of vitrifying.
2. the described method of claim 1 about 9%～about 19% of chargings is an aluminium all wherein.
3. the described method of claim 1, wherein said heating is carried out with reflux type.
4. the described method of claim 1 after described mixing and heating steps, comprises that also glass makes step, and wherein described material being remained on is enough to improve matrix and forms and enough advantageously make carbon from described material under the isolated temperature.
5. the described method of claim 1, wherein said waste tank lining is crushed to less than 6mm.
6. the described method of claim 1 is wherein by the described material of toughened glassization.
7. the described method of claim 1 is wherein used the calcium oxide of q.s, makes CaCO
3Be converted into CaF with NaF fully according to following formula
2, Na
2O and CO
2:
CaCO
3+2NaF→CaF
2+Na
2O+CO
2。
8. the described method of claim 1 wherein adds a certain amount of calcium oxide, makes that the CaO and the ratio of vitrifying material are about 0.04～about 0.10.
9. the described method of claim 1 wherein adds a certain amount of silicon-dioxide, makes Na in the vitrifying material
2O/Si
2O
3Ratio be about 0.21～about 0.36.
10. the described method of claim 1 wherein is heated to described material about 800～about 1200 ℃.
11. the described method of claim 1, wherein said heating are carried out in that fluorine and carbon are retained under the temperature in the described material.
12. the described method of claim 1 wherein is added to glass in the puddle of described material, to increase the cementing property of output and the described vitrifying material of improvement.
13. the described method of claim 1 wherein after vitrifying, arrives about 4000m with described improved grinding
3/ kg～about 8000m
3/ kg.
14. a device, it comprises: (a) first container is used to heat the mixture of waste tank lining, silica source and calcium oxide source, to destroy prussiate, fluoride salt is converted into Calcium Fluoride (Fluorspan) and forms the uniform liquid material; (b) second container is used for physically separating carbon from described material; (c) the 3rd container is used for the described material of vitrifying.
15. the described device of claim 14, wherein said first container are the rotary kiln that is used for the heating of adverse current form.
16. the described device of claim 14, wherein said second container are to be used for that described material is remained on to be enough to increase matrix formation and enough advantageously to make carbon make stove from the glass under the isolated temperature of described material.
17. the described device of claim 14, wherein said the 3rd container is a quenching bath.
18. vitrifying material by the described method preparation of claim 1.
19. fluorine calcium aluminosilicate and fluorine sodium aluminium silicate be mainly amorphous solid substrate, it is made by waste tank lining, carbon content is about 5wt%～about 25wt% less than about 1wt% and Calcium Fluoride (Fluorspan) content, has cohesiveness when being ground to particulate.
20. claim 19 is described to be mainly amorphous solid, it is 95% amorphous that wherein said solid is at least about.
21. claim 19 is described to be mainly amorphous solid, it is 99% amorphous that wherein said solid is at least about.
22. claim 19 is described to be mainly amorphous solid, it is 99.8% amorphous that wherein said solid is at least about.
Be mainly amorphous solid 23. claim 19 is described, wherein said solid is a particle form.
Be mainly amorphous solid 24. claim 19 is described, wherein said solid Bu Laiyin value is about 2000～8000cm
2/ g.
Be mainly amorphous solid 25. claim 19 is described, its weight is composed as follows: about 5～35% CaF
2, about 30～60% SiO
2, about 5～25% Na
2O, about 10～25% Al
2O
3With less than about 1% carbon.
Be mainly amorphous solid 26. claim 19 is described, its weight is composed as follows: about 10～25% CaF
2, about 35～45% SiO
2, about 10～15% Na
2O, about 18～23% Al
2O
3With less than about 1% carbon.
27. claim 19 is described to be mainly amorphous solid purposes, wherein said be mainly amorphous solid with the alkaline activation agent as making concrete binding agent.
28. a composition, it comprises portland cement, described amorphous solid, fumed silica (silica fume) and the slag of being mainly of claim 19.
29. the described composition of claim 28, its comprise about 30～40% portland cement, about 15～35% be mainly amorphous solid, about 2～8% fumed silica (silicafume) and about 20～30% slag.
30. the described purposes that is mainly amorphous solid as the portland cement substitute of claim 19, it measures about 20wt%～about 30wt%.
31. the described purposes of amorphous solid in cement that be mainly of claim 19, its amount is higher than about 90%.
32. the described purposes that is mainly amorphous solid as hydraulic binder of claim 19.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499251A (en) * | 2015-12-11 | 2016-04-20 | 北京京碧蓝环保科技有限公司 | Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond |
| CN109108049A (en) * | 2018-08-01 | 2019-01-01 | 湘潭大学 | Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag |
| CN109133620A (en) * | 2018-10-30 | 2019-01-04 | 袁利民 | Utilize the method for electrolytic cell waste residue production glassware |
| CN112692042A (en) * | 2020-12-08 | 2021-04-23 | 广西博世科环保科技股份有限公司 | Aluminum electrolysis cell waste refractory material treatment process and system thereof |
-
2005
- 2005-02-16 CN CNA2005800481602A patent/CN101119943A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105499251A (en) * | 2015-12-11 | 2016-04-20 | 北京京碧蓝环保科技有限公司 | Glass solidification stabilization method for treating aluminum electrolysis waste slot lining based on F-Si chemical bond |
| CN109108049A (en) * | 2018-08-01 | 2019-01-01 | 湘潭大学 | Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag |
| CN109108049B (en) * | 2018-08-01 | 2021-06-18 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis hazardous waste residues |
| CN109133620A (en) * | 2018-10-30 | 2019-01-04 | 袁利民 | Utilize the method for electrolytic cell waste residue production glassware |
| CN112692042A (en) * | 2020-12-08 | 2021-04-23 | 广西博世科环保科技股份有限公司 | Aluminum electrolysis cell waste refractory material treatment process and system thereof |
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