CN101283064B

CN101283064B - Coated slag

Info

Publication number: CN101283064B
Application number: CN2006800375896A
Authority: CN
Inventors: M·拉贝尔芬格; H·U·施密特; H-J·雷泽; J·雷特纳; A·艾森哈特
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-10-10
Filing date: 2006-10-05
Publication date: 2011-03-30
Anticipated expiration: 2026-10-05
Also published as: WO2007042451A1; EP1940986A1; CN101283064A; JP2009511407A; US20080257108A1; KR20080056254A; DE102005048808A1

Abstract

The invention relates to a coated slag, characterized in that it is coated with a layer of a hydrophobic polyurethane.

Description

Coated slag

The present invention relates to the slag that hydrophobicity urethane coats.

In many technologies, can obtain slag, particularly in metallurgy.Depend on production technique, slag can be divided into blast furnace slag, smelting slag and steel plant slag.Depend on technology, these slags can be produced by metallic ore, coke, Wingdale and rhombspar as by product in actual production process.Blast furnace slag generally is used as cement raw material and is used for Road construction, also is used as fertilizer under the individual cases.The a spot of slightly steel slag that obtains mainly is used in building material field, and is used as fertilizer on the less degree.Sub-fraction, general about 10%, in garbage bury, dispose.

Part steel slag also is used in hydro project except that being used for Road construction.Basic demand about the hydro project stone material has defined in " Technische Lieferbedingungem f ü r Wasserbausteine ", comprise the requirement about rock density, size and weight classification, stone material shape, ultimate compression strength, frost resistance and volume stability.The structure made from grid structure before used slag often substitutes in hydro project at present.Generally, the slag stone material is no longer placed in the mode of complexity but is toppled over arbitrarily.

Using the shortcoming of slag at first is the mechanical stability deficiency.Thereby when people had found to use in hydro project, for example having, 10～20% slag disintegration was very thin particle size.This crushing process is passed in time and is caused almost fluid-tight gluing, thereby constitutes top layer potential breaking point.

In addition, need avoid toxic substance to be discharged into the environment or under the hydro project situation from slag is discharged in the water.As a result, worry to cause to coenosis and simultaneously to the disadvantageous effect of the automatically cleaning ability of water body.

Prior art discloses with plastics bonded slag and has been used for civil engineering work and hydro project.

Thereby DE 1 946 469 has described and has been used for inclined surface, the sealing ply of the inclined surface in the hydro project particularly, and this sealing ply is made up of stone material, slag and tackiness agent.The tackiness agent that uses is pitch and thermoplastics particularly.Prevented that by in tackiness agent, adding plastics sealing ply from flowing away.

U.S. Patent application-please insert numbering-and KR 2002008805 described and in Road construction, use slag and fluoropolymer resin as material.It is said that this is in order to increase the intensity of material.

JP 2001163649 has described and has comprised inorganic materials, for example the compound of the industrial waste of sulfur-bearing melt coating.This provides＜material of construction of 44mm, and it can be used for Road construction, also can be used on coastal region.Prevented the toxic materials outflow by coating, thereby this compound also can be used as material of construction.

JP 53137222 described to porous material for example slag the photocurable coating is provided.The result has improved hardness, thermotolerance and the chemical stability of material.

But KR 2002001916 has described the water cure coating that is used to wrap up silica, glass or slag.This coating is made of sodium polyacrylate.Matrix material has good anti-seawater ability.

JP 2004236546 has described the slag that lime carbonate coats.The slag that will have coating is applied to the seashore or the bottom, allegedly can regulate the pH value of seawater and reduce building cost.

JP 7048187 has described in construction industry and has recycled waste slag by using liquid resin, particularly Resins, epoxy or fiber-reinforced resin to coat.

The shortcoming of described scheme particularly in them usually to the opposing deficiency of environmental influence.This may cause coating destroyed and its advantage is no longer played a role.

Thereby purpose is the slag stone material to be handled make it have high mechanical stability and environmental friendliness.The method that the slag stone material is handled should be simply, reliably.

This purpose can be surprisingly by realizing with hydrophobicity layer of polyurethane coated slag.

The present invention thereby relate to the slag that the hydrophobicity layer of polyurethane coats.

The invention still further relates to the method for producing coated slag, wherein use the liquid starting ingredient coated slag of hydrophobicity urethane, the former is at the slag surface cure.

The slag that uses can be known all types in the industry.Particularly blast furnace slag, smelting slag and steel plant slag.Slag exists with the fragment form of diameter in 0.5～50cm scope usually, preferred 0.5～20cm, preferred especially 2～15cm, particularly 2.5～6.5cm.Can admit of sub-fraction more fine grained chippings until fine dust, because of it can mix in the coating.But the amount of dust should not surpass 10 weight % based on slag, not so may cause the disturbance in the urethane.

Layer of polyurethane on the stone material has only several mm thick usually, preferably is no more than 5mm, and particularly 0.1～5mm is thick.Slag is coated substantially fully.

As mentioned above, the coating of slag is undertaken by the liquid starting ingredient from urethane to slag and the curing thereon that apply.Can arrange slag stone material and it is wetting with the liquid starting ingredient of urethane.Wetting can being undertaken by for example toppling over or spraying also can be mixed and stirred by simple machinery and be carried out, but preferred spray.

Can design this method so that coated slag exists with the form of independent fragment.

Preferably, coated slag exists with the complex body form, and promptly independent fragment is bonded to one another by urethane.The independent fragment of slag is by the urethane tight bond, and bonding only takes place at point of contact.As a result, in the inner hole that forms of molding.

Complex body can be by introducing slag on mould and producing to the liquid starting ingredient that wherein adds urethane, preferably by aforesaid topple over or spray carry out.At least should be enough thereby the size of mould is not crucial make the liquid starting ingredient of urethane can be before it solidifies that whole slags are wetting greatly.Preferably, die size is 100+50 * 100+50 * 15+10cm.

In another embodiment of the inventive method, slag is applied to its stand-by part, for example dike, dam, dyke or traffic route use the liquid starting ingredient of urethane wetting on the spot, and solidify herein.

In another embodiment of the present invention, slag is mixed and stirred with the liquid starting ingredient of urethane in amalgamator.Subsequently compound is drawn off from amalgamator and urethane cures.

The amalgamator that is used to mix and stir the starting ingredient of slag and plastics can be all types of amalgamators in principle, if with its starting ingredient that can make plastics with the basic complete wetting of slag.To have proved particularly suitable be the amalgamator that comprises open containers, the cylinder that for example (preferably has internals).In order to mix and stir, can swing roller or can mobile internals.

This type of amalgamator is known and for example be used in and produce concrete mixture in the construction industry.

If compound directly put on want fixed surface, then can advantageously amalgamator be installed on vehicle for example on tractor, front end type carrier aircraft or the truck.In this embodiment of method of the present invention, compound can be transported to it in each case and will use part.After emptying amalgamator, but the compound manual allocation is for example disperseed by raking.

In embodiments of the present invention, mixing and stirring continuously of the liquid starting ingredient of slag and urethane carried out.For this reason, the liquid starting ingredient of slag and urethane is introduced continuously in the amalgamator and wetting stone material is drawn off continuously.In this program, must guarantee that parent material stays in the amalgamator up to can abundant wetting slag.Be easily, this mixing device can be along treating that fixed section moves with certain speed, and this speed makes and draws off from amalgamator with fixed required amount with the wetting slag of the starting ingredient of plastics.Also can make continuous mixing device in fixing operation down, and the wetting slag that will draw off from amalgamator is transported to desired location.

In another embodiment of the continuous design of the inventive method, amalgamator can be swing roller, to wherein introducing slag continuously.This cylinder is equipped with nozzle, its with the starting ingredient continuous dispensing of plastics to stone material.Here, the rotation of cylinder has guaranteed that plastics and stone material thoroughly mix and stir.So, plastics/slag mixture draws off continuously by the opening of cylinder end.Swing roller can be a level, also can various angles inclinations draw off with promotion.

In another embodiment of continuation method, slag is transported on the travelling belt that moves through the tunnel continuously.The tunnel has opening, and the parent material of plastics is discharged on the slag continuously through these openings.At the travelling belt end, slag falls into the opening mixing cylinder, and it draws off mixture with adjustable transfer rate.

Be narration below about hydrophobicity urethane.

In the context of the present invention, the component of urethane be interpreted as compound very at large with free isocyanate group group and have can with the compound of the group of isocyanate groups reaction.Can be generally hydroxyl or amino with the group of isocyanate groups reaction.Preferred hydroxyl, because amino-reactive is very big, reaction mixture therefore must fast processing.Be commonly referred to as urethane below the product that these component reaction form.

The urethane that uses can be conventional and known this compounds.Urethane reacts with the compound that at least two active hydrogen atoms are arranged by polyisocyanates and prepares.The polyisocyanates that uses can be to be liquid state and the prepolymer with at least two isocyanate groups under all polyisocyanates, mixture and the room temperature in principle.

The preferred aromatic polyisocyanate that uses, the mixture (thick MDI) of the isomer of preferred especially tolylene diisocyanate (TDI) and the isomer, particularly MDI of diphenylmethanediisocyanate (MDI) and polyphenylene polymethylene polyisocyanates.Polyisocyanates also can be modification, for example by introducing isocyanurate group, particularly introduces the carbamate groups modification.After the compound mentioned prepare by polyisocyanates and substoichiometric compound with at least two active hydrogen atoms are reacted, be commonly referred to the NCO prepolymer.Its NCO content is generally in 2～29 weight % scopes.

Generally, usually with the polyfunctional alcohol, promptly so-called polyvalent alcohol or not too preferred polyfunctional amine are as having the compound of at least two energy with the hydrogen atom of isocyanate groups reaction.

In the preferred embodiment of the inventive method, the fine and close urethane of use be endowed hydrophobic those.Hydrophobicity can known hydroxyl-functional component produces in the chemistry of fats by being added at least a starting ingredient of polyurethane system especially, preferably adds in polyol component.

Known a lot of hydroxyl-functional components also can be used them in the chemistry of fats.Example is a Viscotrol C, the oils of hydroxyl modification such as raisin seed oil, black cumin oil, Semen Cucurbitae oil, borage oil, soybean oil, wheatgerm oil, rapeseed oil, Trisun Oil R 80, peanut oil, Prunus amygdalus oil (apricot kernel oil), Pistacia lentiscus benevolence oil, Prunus amygdalus oil (almond oil), sweet oil, Queensland nut oil, Lipoval A, Oleum Hippophae, sesame oil, hazelnut oil, Oenothera oil, wild rose oil, cannabis oil, Thistle oil, Walnut oil., hydroxyl modification and based on Oleomyristic acid, Zoomeric acid, oleic acid, vaccenic acid, petroselinic acid, cis-9-20 carbon acid, erucic acid, Selacholeic acid, linolic acid, linolenic acid, stearic tetraenoic acid (stearidonicacid), arachidonic acid, timnodonic acid, the fatty acid ester of clupanodonic acid and docosahexenoic acid (cervonic acid).Here preferably use Viscotrol C and with the reaction product of oxyalkylene or ketone-formaldehyde resin.After the compound mentioned for example by Bayer AG with title

Sell.

The preferred in addition known polyvalent alcohol in chemistry of fats that uses can be by making epoxidised lipid acid ester open loop and simultaneously and the alcohol reaction, and if suitable further transesterification reaction and obtaining subsequently.Hydroxyl is introduced in oil or the fat main, the epoxide group of formation is reacted with monohydroxylic or multi-hydroxy alcohol carry out by making the olefinic double bond epoxidation that exists in these products.Obtain hydroxyl or under multi-group alcohol's situation, obtain having the structure of a plurality of OH bases from the epoxide ring.Because oil ﹠ fat is generally glyceryl ester, therefore parallel transesterification reaction also takes place under above-mentioned response situation.The compound that so obtains preferably has the molecular weight in 500～1500g/mol scope.Such product can obtain by for example Henkel reaction.

In the particularly preferred embodiment of the inventive method, the fine and close urethane that uses be can by polyisocyanates with have those that the compound reaction of at least two energy with the hydrogen atom of isocyanate groups reaction make, the compound that wherein has at least two active hydrogen atoms comprises the aromatic hydrocarbon resin, particularly indenes/coumarone resin of known polyvalent alcohol and at least a phenol modification at least a chemistry of fats.Thereby these urethane and component thereof have high hydrophobicity in principle even can solidify under water.

The aromatic hydrocarbon resin of the preferred phenol modification of using with terminal phenolic group group is the indenes/coumarone resin of phenol modification, the cuts of aromatic hydrocarbons resin especially, particularly comprise general formula (I) compound as those of basal component:

(I)

Wherein n is 2～28.This type of product can buy and by R ü tgers VTF AG for example with trade(brand)name Supply.

The aromatic hydrocarbon resin of phenol modification, the particularly indenes/coumarone resin of phenol modification have the OH content of 0.5～5.0 weight % usually.

The aromatic hydrocarbon resin, particularly indenes/coumarone resin of known polyvalent alcohol and phenol modification preferably use with 100: 1～100: 50 weight ratio in the chemistry of fats.

Can use other to have the compound of at least two active hydrogen atoms with described compound.Because the stability to hydrolysis height of Aethoxy Sklerol, it is preferred.They can be by conventional known method preparation, and the addition reaction by oxyalkylene and H-functional starter substance prepares usually.The Aethoxy Sklerol of Shi Yonging preferably has and is at least 3 functionality and is at least 400mg KOH/g simultaneously, preferably 600mgKOH/g, the particularly hydroxyl value of 400～1000mg KOH/g at least.Trifunctional initial substance and reactions of alkylene oxide prepare by making at least in a usual manner for they.Spendable initial substance is preferably the alcohol that has at least three hydroxyls in the molecule, as glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder or sucrose.The preferred oxyalkylene that uses is a propylene oxide.

Can be with other conventional ingredients, for example catalyzer and conventional auxiliary agent and additive join in the reaction mixture.Especially, should in reaction mixture, add siccative, zeolite for example, thus make polyurethane foam to avoid water in component, to accumulate.These materials preferably add in the compound of the hydrogen atom with the reaction of at least two energy and isocyanate groups.This mixture is at the industrial polyol component that often is called as.For improving the permanent stability of mixture, add the reagent that can prevent microbiological attack also advantageously.And adding UV stablizer helps avoiding the embrittlement of molding.

The urethane that uses can prepare in the presence of catalyst-free in principle.Solidify for improving, can use catalyzer simultaneously.The catalyzer of selecting should preferably can cause those of long as far as possible reaction times.As a result, reaction mixture can keep liquid for a long time.Such as description, also catalyst-free operation fully in principle.

Polyisocyanates is answered so that isocyanate groups above ratio that stoichiometry exist carry out with the combining of compound of the hydrogen atom of isocyanate groups reaction with having two energy at least, preferably surpasses at least 5%, particularly surpasses 5～60%.

The characteristics of the preferred hydrophobicity urethane that uses are its good especially workabilitys.Thereby these polyurethane surfaces reveal good especially binding property, especially for the substrate of humidity, as wet rock, particularly grouan brickbat.Although there is water to exist, the curing of urethane is carried out with fine and close in fact form.The fine and close urethane that uses even under the thin layer situation, also show complete compact curing.

Therefore the preferred urethane that uses be particularly suitable for the fixed of the fixed of dike, particularly dam and dyke.Bonding between rock and the urethane is very strong.In addition, particularly when using very hydrophobic urethane, urethane does not almost have hydrolytic deterioration, therefore has very long weather resistance by the fixed dike of the inventive method.

Be to implement the inventive method, preferably with polyisocyanates with have the compound of at least two active hydrogen atoms, and this mixture and stone material are mixed and stirred.Also two kinds of starting ingredients of urethane separately can be joined in the stone material and then with them in principle and mix.Yet the mechanical property deficiency that therefore inhomogeneous mixing also causes urethane may appear in such cases.

The starting ingredient of urethane can mix by known way.Under the simplest situation, component can be introduced container with required ratio, in bucket, mix by simple agitation, in mixing apparatus, mix and stir then with stone material.Also can be in polyurethane chemistry common hybrid component, for example in the mixing head, mix the starting ingredient of urethane, this mixture is contacted with stone material.

By the hydrophobic treatment of urethane, can suppress its hydrolysis and decompose.Therefore coating has the almost unlimited life-span.

The result who coats with hydrophobicity urethane is not have the soluble metal compound and discharge from slag.Therefore the slag that coats can be used for all application, especially for hydro project.

Coated slag according to the present invention has high strength and can be extensive use of.It both independently the stone material form use, form that also can complex body is used.

The advantage of complex body in hydro project be its high strength particularly.In addition because the hole of their inside and thereby the water permeate that has, they can absorb the energy of wave, thereby provide effective protection for embankment.

Claims

1. the coated slag that is coated by the hydrophobicity layer of polyurethane, the diameter of wherein said slag is 0.5～50cm.

2. according to the coated slag of claim 1, wherein the thickness of layer of polyurethane is no more than 5mm.

3. according to the coated slag of claim 1, wherein the thickness of layer of polyurethane is 0.1～5mm.

4. according to the coated slag of claim 1, wherein slag granules obtains molding by the urethane bonding.

5. according to the coated slag of claim 1, wherein the preparation of urethane is undertaken by polyisocyanates is reacted with the compound with at least two active hydrogen atoms.

6. according to the coated slag of claim 5, the compound that wherein has at least two active hydrogen atoms comprise at least a in chemistry of fats known hydroxyl-functional component.

7. according to the coated slag of claim 5, the compound that wherein has at least two active hydrogen atoms comprises the indenes/coumarone resin of at least a phenol modification.

8. method of producing coated slag is wherein used the wetting slag of liquid starting ingredient of hydrophobicity urethane, and the former solidifies on the slag surface, and the diameter of wherein said slag is 0.5～50cm.

9. method is according to Claim 8 wherein passed through the liquid starting ingredient wetting slag of spray with hydrophobicity urethane.

10. method according to Claim 8 is wherein by toppling over the wetting slag of liquid starting ingredient with hydrophobicity urethane.

11. method according to Claim 8, the wherein wetting slag of liquid starting ingredient of usefulness hydrophobicity urethane in amalgamator.