CN1154711A

CN1154711A - Method and device for recycling waste by pyrolysis and reduction

Info

Publication number: CN1154711A
Application number: CN 94193520
Authority: CN
Inventors: 克劳德·福汀
Original assignee: ETI Co Ltd
Current assignee: ETI Co Ltd
Priority date: 1993-09-24
Filing date: 1994-09-20
Publication date: 1997-07-16

Abstract

A low-energy, non-polluting method for reducing waste, and associated plant, are disclosed. Waste such as worn tyres, lead-acid batteries, old oils, sawdust, papers, rags, plastics, etc. are recycled directly as industrial quality secondary products or indirectly by reaction with the decomposition vapours of the above. A plant for implementation of said method will consist essentially of a large multi-wall furnace under different stages of vacuum, heating elements and one or more fluid ring pumps providing a reaction with the volatile matter. Continuous processing can be achieved by associating liquid waste with divided solids. A high temperature device breaks down the complex volatile matter and backscatter.

Description

Utilize the method and apparatus of waste again by cracking and reduction

The present invention relates to handle waste method, handle with equipment and the product that obtains.Method of the present invention is pollution-free, energy-conservation and can not produce final waste.Described waste can be finely-divided solid, mashed prod or liquid form.These wastes can be the intermediate material or the final materials of contaminated natural product (natural), animal, organism, fibrous material, synthetics or chemical substance.

At first, this method reduces the volume of waste.More particularly, this method produces and is separated as dehydration or dry the non-activity material that remaining removing is polluted, or combustible solid residue.In fact, according to the method, waste is carried out physics and chemical treatment completely, they can re-use in various circulations and sintetics as a result.

At present, when waste is made up of combustiblematerials, burned with recovered energy in some situation sometimes.Developed the method for cracking waste, but the outlet of resistates is not provided, necessary discharging, and these methods can be produced harmful or even Hazardous substances.Breaking test carries out under vacuum or partial pressure on a small scale, but they do not provide the method for removing gas phase.In addition, do not carry out any industrial application more yet.

The present invention to depress by the method for pyrolysis processing waste similar in preliminary vacuum or branch.The equipment of this method comprises a special cracker, draws off the drying solid resistates of the degassing fully from cracker, extracts all liquid or volatilizable component thus and makes itself and a kind of auxiliary fluid that pumps into carry out building-up reactions.In addition, reinject at last that its residue vapor makes it or in cracker or in a parallel device, react with auxiliary fluid.

As first embodiment, the tire that the present invention is applied to degrade.Here it is, through shearing tire cut into the volume that two portions or three parts can increase waste, and this waste is handled by cooperating heat, pump into, circulate auxiliary fluid and circulation residue vapor.Equipment according to the inventive method comprises the special vacuum oven that links to each other with utility appliance with particular form, as following shown in Figure 1.

Used tire is pulverized with the abendoned oil that adds in the container (1) of sealing, and the material that will pulverize is being depressed and is being collected under control air pressure in branch before by cracker/reducer (2).Conveying between this stream oriented device is carried out in vertical tube by excessive oil, and oil plays the balance fluid pressure differential and the effect of sealing is provided.In cracker/reducer, the temperature of the material that will pulverize rises to minimum 860 ℃, and to avoid forming mixture such as dioxin (dioxin), gas phase can be by effective and extracting continuously like this.Steam passes through the pump extracting with auxiliary fluid (3).Here also be as auxiliary fluid with oil.Simultaneously, the steam reaction that this oil will be directly goes out with extracting makes the hydrogenation or make its part by isomerization once more of its quilt in this way.Be blended under the suction static pressure and carry out, in " the Special Mixed device " of the device effect that reacts, carry out but be emulsified under the power pressure.Can improve hydrogenant productive rate again by the catalyzer of regulating the oil temperature and add in fluidised catalyzer or the solution.After hydrogenation was finished again, cooled residue vapor was made of uncondensed gas, and uncooled gas is reinjected in the cracker so that cracking therein.Help this " scene " cracking by temperature in the cracker and initial vacuum.Cracking is settled out high pure carbon, and it can reclaim separately.Cracking also discharges hydrogen, and hydrogen is directly with the material that pulverizes with from the steam reaction in its extract.Used oil can also directly steam in container so that cracking in treating processes.

The solid waste that produces in the aforesaid method is carbonaceous powder and the mixture that comes from the steel fiber of tire.With this resistates cooling, in autothermic cracking device/reducer, preventing under the carbon dioxide atmosphere of air admission then, get rid of along the device that the cooling transfer lime is delivered to vibrating bed separator (4) from vacuum vessel by making it.In case after steel fiber separates from powder, powder sieved and be stored in big packing bag or the special container (5).For the amount of finish of one ton of tire per hour, the amount that required and gas phase are carried out blended oily fluid (6) is about about 100 tons.Oil depot is made up of several about 60,000 liters jars, and the dead space in each jar is full of carbon dioxide, residue is pressed reach 20mbar.These jars link to each other with the special discharging platform (7) that is equipped with.This oil is also as heat-conducting fluid.

Just in case accident occurs, make the equipment inactivation with carbonic acid gas.Cracker/reducer is equipped with cooling system (8), and it is used for heat insulation material input oil depot is played the buffered effect.All the time carbonic acid gas (9) is all stored so that the passivation when stopping of cracker/reducer adding to depress nearby, and, usually for the security consideration when occurring catching fire.Therefore oil tank is positioned on the carbonic acid gas pipeline limit.

The equipment of the inventive method generates decolorizing carbon and the steel fiber that comes from tire by using abendoned oil when being applied to handle tire.These fiber separate easily because resistates be complete drying and segmented.For the steel fiber that obtains according to the inventive method, kept their useful mechanical propertys and can be used in the spray concrete or be used for inserting wear-resisting and the plate of anti-the disruptive.These fibers especially can add in the strong concrete composition with extruding in the prefabricated process molded.These fibers can be used as body plan and have the matrix material that aluminium, magnesium, lithium or low melting point make the matrix light weight, and the preparation method is similar to sintering.

After isolating steel fiber, resistates carbon containing (greater than 92%) and mineral element are as the material (SiO relevant with loading material of rubber ₂, MgO etc.), and obviously contain the segmentation shape be used for sulfurized zinc, therefore this resistates can be used for preparing new rubber product.Produce big specific surface area with the chemical bond cracking that discharges volatile matter in this resistates, this resistates can be used as " activated carbon " in preparation absorption filtering material or purifying bed.

Tire, rubber and plastic refuse, great majority be derived from the resistates and the filamentary materials (as sawdust, paper, rag etc.) of oil, when they during cracking, also can produce big specific surface area according to the inventive method under vacuum.In addition, the advantage that all these carbonaceous resistatess have is their not sulfur-bearing and chlorine, therefore if when they finally are used as fuel, and can burn cleanly and do not have the danger of formation dioxin (dioxin).

Another similar equipment can be used for handling aluminium sheath cable and aluminium foil (no matter whether scribbling plastics).In this way, obtain the mixing resistates of carbon containing and aluminium and can sinter this resistates into rod, to be formed for the fuel electrode in metallurgy and the electrometallurgy.

Vacuum oven (center cell in cracker/reducer) must be big.It is characterized in that its inner vessels comprises several non-leakage coaxial wall, vacuumizes stage by stage between wall.These outer walls can partly play the effect of thermal baffle, the stress that each dividing plate absorption portion produces because of normal atmosphere.Many parts of an one or more or outer wall of these outer walls can be fixed on together, or the material of available poor thermal conductivity such as porous material (preferred aperture material) replacement.The fixed cap of one each vacuum outer wall of cover sealing is used for load.Space between two lids in two outer walls comprises that one " sealed cabin " is to regulate vacuum and can allow load in operation.Same equipment might draw off residual thing from " degraded ".

For helping to load and discharging, the air lock can be independently with separable.These air locks can comprise tradable container, this container by means of flange by being connected on the main closed container with provision for sealing linkage interface independently.Yet better is the effect that can play continuous duty.Difficulty is promptly carried between the container under the different vacuum capacities particularly in waste is carried (or the output of autothermic cracking device core) to core continuously.The invention provides fluid add is wanted solution in the cleaved solid waste, for example, when with the tire that pulverizes, can be oil.The waste of being made up of separating solid substances is fluidized to a certain extent like this.Conveying is carried out continuously by means of pipeline and by the path of self-compensating pressure difference.Liquid phase is also guaranteed sealing.

In stove, heating installation can be the form of center irradiation light.In the embodiment of Z-axis Container Type, the midfeather that is the funnel form also can play the effect of hot-plate, this plate farthest with the thermal insulation of inner vessels shell.In the simple embodiment, the steam extraction pump is a Pendular ring type, and discharging in slurry tank or container.Yet the better implement scheme is by keeping under the air chamber ultimate situation in the pump, through injection and/or spray and force auxiliary fluid recirculation and finish as the mode that strengthens pump efficiency.Play effect on the whole: steam that pumps into and auxiliary fluid for biphase dynamic response device.Reaction efficiency will improve by the condition of catalyzer in control fluidic temperature and/or the solution or fluidized catalyst.After emulsion output and sedimentation, residue vapor can be extracted out from the sedimentation container successively so that handle with another kind of auxiliary fluid in second reactor, to be transfused in second container with stylish emulsion, in this container, pass through another reactor for treatment residue vapor, and the like.

Conveying and sedimentation container can be bonded with each other, and can play the effect in the stage of leaving standstill.Along with the gradient from core to outside wall temperature reduces, the container that comprises continuously mutually might be based on different enthalpy amount classifications (also can pass through the density separation in each container) therein.Residual gas also can filter on the activated carbon filter, and this filter can be produced and reclaim by equipment itself.At last, residual gas can be at high temperature or is reinjected in the cracker by the intermediary element of the very high equipment of temperature.This equipment can be positioned at the center of cracker, and forms the gradient part of rising waste temperature thus.Cracking will discharge the reactive component of " in core " reaction.This cracking also can form precipitation, and as carbon, this carbon can be by greying.

Several gas phases that dividing potential drop is different can use several pumps according to auxiliary fluid or fluidic character and temperature extracting under different condition simultaneously.From the steam of each phase after special processing, in the cracker that reinjects or inject parallel equipment.Another high temperature service that forms steam accumulator can place between cracker and extraction pump or the pump, and this steam storage device can produce ejecta and get back in the fluid that dispersive makes progress at suction surface.The suction surface of steam and residual gas can be loaded onto provides pyritous device such as induction heating device plural components is cracked into corresponding free radical.

According to the inventive method and by unique way, except the cracking resistates and vapor phase is extracted from waste.This gas phase is handled and processed with the recombinant of avoiding any hazardous material or synthetic.Synthetic can being undertaken by the physics and the chemical reaction of this vapor phase and one or more kind auxiliary fluids.This method also can be used for the hydrogenation again of oil in a manner described.

At last, though the cracking of residue vapor might obtain high-purity throw out such as sulphur, carbon or graphite (even intermediate phase graphite), cracking always discharges the volatilization phase of being made up of reactant gases such as hydrogen or chlorine, and this reactant gases is with in equipment or solid residue in another parallel equipment and extracting steam direct reaction and interact.

By cooperating several equipment,, can carry out the chemical reaction that do not observe in other occasion such as hydrogenation, chlorination, synthetic, reduction etc. for the residue vapor or the fluid that interact and produce.These embodiments according to the inventive method will appear at processing plastics or lead storage battery waste especially.

Come from plastic material such as bottle for processing, the vehicle waste thing of packing material, crushing, the equipment of the inventive method can make direct processing carry out, and do not limit the kind of plastics in advance.The plastics that pulverize can be carried continuously by the cold water post.In carrying out cracking process, utilize the special auxiliary fluid of chlorine that absorbs monomer or come from decomposed P VC by parallel pump extracting steam, this steam is carried out the separating treatment and the residual gas that reinjects.

Hold the situation in pond for handle used batteries and other lead according to the inventive method, do not need to anticipate (turned letter, pulverize, with plastics from put with isolator separate).Cooperating heating and aspirate with pump can extracting sulfur-bearing and sulphur steam.These steam are dissolved in auxiliary fluid (sour water of dissolving sulfur-bearing steam), inject simultaneously and contain the residue vapor of sulphur steam with oxidation of sulfureted lead.Shell is cleaved.Plumbous and the lead oxides power of relying on for support draws off and segregate into the crucible of accepting that places under the stove plate by different densities.Yet in a special embodiment, use heating crucible, or in embodiment more specifically, by the direct induction heating lead bath of low frequency to guarantee induction stirring.According to an embodiment of present method, plumbous and plumbous oxide can be drawn off continuously.Rong Hua lead will flow in the arm (arm) of " U " shape crucible or flow in the arm of crucible of the separates walls with effect same like this, and another arm is a unloading arm.Liquid lead will provide sealing and provide the fluid static balance by the difference amount in two arms between two arms simultaneously, and mechanical means is carried oxide compound by lead bath simultaneously, but because, oxide density is low can to rise to the surface, in this recovery.

Remaining sulfur-bearing quantity of steam is big, can be oxidized to sulphur steam and acid by catalysis method.Therefore, in a simple application of the inventive method, production lead capable of circulation, plumbous oxide and sulfuric acid.Yet it is more economical and useful making the residue vapor interaction from aforesaid a plurality of equipment.That is: the hydrogen of tire material that pulverizes from processing and the cracking incondensable gas in oil part can be settled out sulphur and/or plumbic oxide is reduced to minimum plumbous oxide or lead from sulfurous gas.On the contrary, when handling with abendoned oil from the cracking steam of the tire material that pulverizes, the sulfurous gas part can be used to separate the aromatics carbide of formation.In addition, the sulfur-bearing steam in the solution can be that set comes leisure to handle the auxiliary fluid of the chlorine of cracking PVC in the equipment of plastic material.Can be used for handling in the like device of waste for the SULPHURYL CHLORIDE of producing above and chlorine steam and can be used for handling contain titanium dioxide resistates to produce the muriate of titanium, this muriate is successively by magnesium reduction.

Though in some of the inventive method used, the product of production was not too important, can directly be re-used or almost directly re-use or act as a fuel as them and be burnt, some the time dehydration, inactivation or decontamination be enough to reach purpose.

So the equipment of the inventive method can design to be handled from the animal slaughtering and the body and butchers the thing waste.This equipment is further cracking vapor portion (novel method of head it off is provided) not only, and might control solid waste cracked degree, can obtain variant production like this, until producing " animal black ".

After the same method, equipment can be to from the waste of potato starch production, broken mill, extruding and stilling chamber such as the dehydration of potato peel, beet pulp etc.Steam can by fractionation simultaneously flammable dried residue extrude the flammable timber of formation continuously with after binding agent such as heavy fuel oil mix.

Equipment also is fit to the pre-treatment domestic refuse.The exsiccant resistates can be stored and burning in the winter time in summer, and the exsiccant resistates is cleaning and available its production hot steam.

Equipment also be particularly suitable for handling petroleum residue or even be fit to the distillation petroleum component: it can use crude oil, and consumption and petroleum residue and the auxiliary fluid that finally pumps into are as many.In such a way, can carry out the cracking cracking, the fractionation of cracked hydrocarbon and reorganization.According to various power operation conditions, the composition that is used for the catalyst type of dynamic response device and the hydrocarbon of adding (Hydrocarbides) can the various types of hydrocarbon that distillate of direct production, for unwanted cut, no matter gaseous state or liquid state can circulate in equipment as resistates or additive fluid.

Last residual inert sludge is handled in the treatment facility of the inventive method.Slurry is extracted out continuously, and dehydration is also only carried out high temperature evaporation to dried residue under very low temperature, then the condensation heavy metal.In equipment simultaneously respectively extracting go out cold and hot steam.Cold steam is easy only by the pipeline condensation by pump, and will at high temperature pass through centre or relevant device cracking by the hot steam that complicated evaporated product is formed.

Elimination constitutes the special applications of the inventive method from the pollution of the waste of sanitary facility.Prerequisite is that the vacuum cracking equipment of short run can be handled.After inerting and reduction 1/3rd, this waste can be handled by the mode identical with handling domestic refuse.Pyrolyzer plays the effect of compactor, and it is under the slight negative pressure when loading.In this embodiment, the squeeze piston head plays the effect of the heating lamp that contains steam Pintsch process device, and these steam then are chlorinated in extraction pump.

Summary is got up, and that the inventive method has is pollution-free, energy-conservation, the dehydration of extracting steam, steam distillation and advantages such as processing, the degassing or inerting cracking waste, and this method can redesign the conventional treatment method into other waste.

Claims are according to the modification of the 19th of treaty

One kind under basic vacuum or the waste branch depress the method for continuous cracking, this waste can be middle waste or final waste, it can be the pollutent in any source, can be natural product, animal, organic, fiber, synthetic or chemical waste, this waste can be pasty state, liquid or finely-divided solid, it is characterized in that making the steam of extraction and the auxiliary fluid that pumps into to carry out physical reaction, fluid is fit to the temperature and the character of steam, and steam can contact with the catalyzer in the fluidized catalyst solution.

2. according to the method for claim 1, it is characterized in that under different condition according to the difference of the character of suction temperature and each auxiliary fluid and temperature with a plurality of pumps extractings simultaneously cracked steam progressively.

3. according to the method for claim 1 and 2, it is characterized in that with from the residue vapor that one or more auxiliary fluids the carry out physical-chemical reaction cracking in equipment or another the parallel equipment of reinjecting.

4. according to the method for claim 1 and 2, it is characterized in that the fluid from two phase reaction is used as auxiliary fluid in another pump, make itself and another vapour-phase reaction.

5. be used to implement the equipment of the arbitrary method of claim 1 to 4, it is characterized in that the part that comprises that many walls vacuum oven is formed is used for the shell of isolated vacuum, two continuous walls that wherein form vacuum can be replaced by the material of poor thermal conductivity or be fixed to, stove links to each other with heating installation on the one hand, the waste material that this heating installation generation is used to heat the needs processing is to produce thermograde, on the other hand with one or more flat

Statement when revising according to the 19th of treaty

A kind of pump parts are absolutely necessary for reaching vacuum in the pyrolysis container.Often, the steam of extraction just is discharged in the atmosphere after simple filtration.When relating to big flow, adopt aeration method to wash these steam.

As the pump parts, can use the water flow jet pump that supplies water by service pump.In groove, spray the washing that to implement to extract steam simply.This known configuration is beneficial to the condensation of water vapor, can also temporarily dissolve some gas, but this configuration can not make the aeration liquid that extracts steam and should obtain purifying that real chemical reaction takes place.

Wherein a kind of configuration of the inventive method comprises a specific pump that links with annular liquid impeller pump and built-in impeller pump, these pumps combine and reach place adapting with this pump, standby liquid with extract steam and carry out the needed physical condition of chemical reaction.Described standby liquid is special in nature, and is the composition that extracts steam.

Except the pump parts, this method comprises other invention configuration, and these are configured on the whole or make contributions to implementing present method separately.

Claims

One kind under basic vacuum or the waste branch depress the method for continuous cracking, this waste can be middle waste or final waste, it can be the pollutent in any source, can be natural product, animal, organic, fiber, synthetic or chemical waste, this waste can be pasty state, liquid or finely-divided solid, it is characterized in that making the steam of extraction and the auxiliary fluid that pumps into to carry out physical reaction, fluid is fit to the temperature and the character of steam, and steam can contact with the catalyzer in the fluidized catalyst solution.
2. according to the method for claim 1, it is characterized in that under different condition according to the difference of the character of suction temperature and each auxiliary fluid and temperature with a plurality of pumps extractings simultaneously cracked steam progressively.
3. according to the method for claim 1 and 2, it is characterized in that with from the residue vapor that one or more auxiliary fluids the carry out physical-chemical reaction cracking in equipment or another the parallel equipment of reinjecting.
4. according to the method for claim 1 and 2, it is characterized in that the fluid from two phase reaction is used as auxiliary fluid in another pump, make itself and another vapour-phase reaction.
5. be used to implement the equipment of the arbitrary method of claim 1 to 4, it is characterized in that the part that comprises that many walls vacuum oven is formed is used for the shell of isolated vacuum, two continuous walls that wherein form vacuum can be replaced by the material of poor thermal conductivity or be fixed to, stove links to each other with heating installation on the one hand, this heating installation produces and is used to heat the waste material of needs processing to produce thermograde, with one or more parallel or use the pump of the serial operation of auxiliary fluid to link to each other with at least one pump wherein, last pump links to each other with the sedimentation container with the jar of circulation auxiliary agent and reacting fluid on the other hand.
6. according to the equipment of claim 5, it is characterized in that it is separable that product is carried sealed cabin, it comprises interchangeable container, and these containers are by flange, by linking to each other with main vessel with the linkage interface of independent enclosed appts.
7. according to the equipment of claim 5, it is characterized in that and to pass through to add the fluid fluidisation by the cracked waste, conveying between two vacuum tightnesss is carried out in pipeline continuously by fluid, and liquid is guaranteed to seal and is used for compensatory pressure difference or poor by the vacuum tightness of side-play amount.
8. according to the equipment of claim 7, it is characterized in that waste oil added in the tire material that pulverizes and other rubber or synthetic waste or oil or the carbonaceous refuse in case with it under vacuum continuously in the input cracker.
9. according to the equipment of claim 7, it is characterized in that the water of sulfur-bearing is added in lead battery and the store battery so that it can be imported in the cracker under vacuum continuously.
10. according to the equipment of claim 7, it is characterized in that solution with SULPHURYL CHLORIDE adds in the waste of titanium dioxide so that can be under vacuum continuously in the input cracker with it.
11. according to the equipment of claim 5, it is characterized in that some cracking products are passed through liquid bath: for example plumbous oxide is removed by the plumbous machinery of fusing.
12., it is characterized in that solid cracking resistates is drawn off through extruding by injecting binding agent such as heavy fuel oil (HFO) and combustible waste material according to the equipment of claim 5.
13., it is characterized in that the device of high-temperature is arranged at from lysate extracting steam and/or is arranged at the residue vapor place of reinjecting very much according to the device of claim 5.
14. according to the equipment of claim 5 and 13, it is characterized in that high temperature is counter disperses or the container unit that reinjects is adjacent with the cracker core or be arranged among the cracker core so that the thermograde of cleaved waste raises.
15. according to the equipment of claim 5 and 14, it is characterized in that the compacting screw head plays the effect of heating lamp and cracker,, be used for the pollution of compacting waste and elimination waste with extracting steam.
16. according to the equipment of claim 5, it is characterized in that by force to inject and/or the fluid re-circulation of ejection replenish at least one pump that uses auxiliary fluid so as to obtain better pump efficiency and with the efficient of steam reaction.
17. according to the equipment of claim 5, it is characterized in that two sedimentation closed containers be included in mutually wherein constitute one the step leave standstill, wherein thermograde from core to outer reduction.
18. carbon-containing residue and flammable agglomerate is characterized in that utilizing the method by in the equipment of claim 5, make from organic, Mierocrystalline cellulose, plastics or rubber waste and other petroleum residue.
19. be used for the carbon-containing residue of absorption filtering material or purifying bed, it is characterized in that utilizing by the method in the equipment of claim 5 making from organic, Mierocrystalline cellulose, plastics or rubber waste and other petroleum residue.
20. the mixed waste of rod is gone in carbon or plumbous agglomeration, it is characterized in that utilizing by the method in the equipment of claim 5 being made by the plastics of waste as insulation aluminium cable and coating aluminium foil.
21. the mixture of carbonaceous refuse and steel fiber is characterized in that utilizing by the method in the equipment of claim 5 being made by rubber and/or exhausted tire waste, resistates reclaims after can sieving in the rubber product preparation.
22. spraying, casting, molding or the concrete of extruding, the steel fiber that it is characterized in that utilizing waste by aforementioned claim to separate the high-carbon content that produces is strengthened described concrete.
23. based on the matrix material of aluminium, magnesium, lithium or light alloy, it is characterized in that strengthening or premolding by the steel fiber of embedding, steel fiber separates from waste by claim 21.
24., it is characterized in that utilizing making by old lead storage battery by the method in the equipment of claim 5 based on the heavy concrete of plumbous oxide.
25. fibre-reinforced heavy concrete is characterized in that utilizing the method in claim 5,22 and 24 the equipment to be made by old lead storage battery and exhausted tire.
26. store the container of the final waste of radioactivity, it is characterized in that they are made by the heavy concrete of claim 24 or 25.
27. winterized stearin is characterized in that utilizing the method by in the equipment of claim 5 again, makes with the cracking steam of rubber waste and waste oil reaction.
28. graphite is characterized in that utilizing by the method in claim 5,13 and 14 the equipment making from the residue vapor Pintsch process of handling the hydrocarbonaceous waste.