CN102149526A - Method for producing pulverized waste plastic and solid fuel or mineral reduction material - Google Patents
Method for producing pulverized waste plastic and solid fuel or mineral reduction material Download PDFInfo
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- CN102149526A CN102149526A CN2009801351801A CN200980135180A CN102149526A CN 102149526 A CN102149526 A CN 102149526A CN 2009801351801 A CN2009801351801 A CN 2009801351801A CN 200980135180 A CN200980135180 A CN 200980135180A CN 102149526 A CN102149526 A CN 102149526A
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- waste plastics
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- firming body
- fusion
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Provided is a method for producing a pulverized waste plastic wherein it is possible to produce at a low cost and with improved productivity a pulverized product by micropulverization of waste plastic. The method for producing a pulverized waste plastic is characterized in that waste plastic is kneaded at a shear speed of 100 (1/second) or greater as it is being melted at a temperature that is the softening and melting temperature or greater, preferably 160 DEG C, but is a temperature at which flammable decomposition gases are not generated, preferably 270 DEG C or lower, and then is cooled and solidified and the solid product is pulverized. Melting and kneading are preferably performed using an extruder, particularly a biaxial extruder.
Description
Technical field
The present invention relates to be used for the waste plastics recycling processing is made the manufacture method of the waste plastics crushed material of ore reduction material, solid fuel etc.
Background technology
In recent years, as being used for the solution that waste plastics effectively utilizes, inquiring into the method for making ore reduction material, solid fuel etc. by waste plastics.If this is because with the plastics fine-powdered, and then its flammability will obtain the leap raising, become useful fuel source.
Plastics are converted into solid-fuelled technology in the past for example to be had directly with the plastics broken method (for example, with reference to non-patent literature 1) of pulverizer fine powder.But during this method, duroplasts can only be crushed to the granularity of 1~2mm, and this pulverizing needs extremely many time and expense, and plastics fibrous, the film shape are difficult to be pulverized, therefore pulverize the problem that exists operation to complicate etc. separately behind the melting and solidification again.
In addition, though known if the waste plastics fine powder is broken, then can make it become generating with the spendable fuel of combustion furnaces such as boiler (for example, with reference to patent documentation 1), but do not put down in writing breaking method in the patent documentation 1 especially, do not have the open relevant technology that improves the grindability of waste plastics itself.
Known to the plastics excellence below the solid fuel particle diameter 2000 μ m, available dry type comminuting method, case of wet attrition manufactured (for example, with reference to patent documentation 2).Though especially think that as the method that obtains fine powder comminution by gas stream, vibratory milling method are preferred, but still the unknown relevant technology that improves the grindability of waste plastics itself.
On the other hand, when for example using from discarded waste plastics such as family as blast furnace during with the reducing material of reducing material etc., fuel, owing to sneak into the chloride plastics of polyvinyl chloride (below be designated as PVC) etc. in the waste plastics, so directly use then produces hydrogen chloride etc., the problem of existence corrosion stove etc.Therefore, the known chloride plastics such as PVC that will contain separate and remove and implement granulation and handle, thereby obtain the technology (for example, with reference to patent documentation 3) of granular plastic shaped body.
In addition, as after chloride waste plastics implemented dechlorination handling with the technology of waste plastics fine-powdered, known to behind waste plastics heating, dechlorination processing, the cooling curing, carry out the broken and technology such as (for example, with reference to patent documentation 4, patent documentations 5) in the input stove of fine powder.
Patent documentation
Patent documentation 1: Japanese kokai publication hei 7-119922 communique
Patent documentation 2: Japanese kokai publication hei 4-332792 communique
Patent documentation 3: TOHKEMY 2002-67029 communique
Patent documentation 4: Japanese kokai publication hei 11-192469 communique
Patent documentation 5: TOHKEMY 2006-241442 communique
Non-patent literature
Non-patent literature 1:PLASTICAS, Vol.47, No.7, p60,1996
Summary of the invention
In general plastics resistance to impact excellence, therefore directly pulverizing is unusual difficulty, when especially being crushed to the following particle diameter of 0.5mm, adopt prolong the pulverizing time, repeatedly overlapping investment is in the method for pulverizer etc.In this case, because the type of pulverizer, plastics become heated condition because of shearing heating in pulverizing, fusion takes place sometimes, or the product of pulverizing become fibrous phenomenon.For preventing this phenomenon, can consider to cool off pulverizer or crushed material, but can increase cost of equipment or operating cost like this.
As the broken method of the fine powder of plastics, so-called freezing pulverizing also is an effective method.That is, cause the temperature province of brittle crush, for example arrive till subzero tens of degree behind the cooling plastic method of pulverizing at general plastics.But this method in advance must cooling plastic, therefore increases cost of equipment or operating cost.
If according to being the fusion dechlorinating process of the so-called waste plastics of representative with the method described in described patent documentation 4, the patent documentation 5, the then PVC carbonification after the dechlorination and embrittlement is so can improve grindability on the whole.But, need carry out handling the processing of the chloride exhaust that produces, the cost height because of dechlorination.Can effectively utilize as hydrochloric acid though can retrieve self-purging chlorine, but still cause the increase of equipment cost.Mince for making the waste plastics fine powder at an easy rate, importantly reduce equipment cost and boost productivity.
Thereby, the object of the present invention is to provide a kind of manufacture method of waste plastics crushed material, it can solve the problem of above-mentioned conventional art, can obtain crushed material with the broken waste plastics of low-cost fine powder, and the productivity ratio of crushed material improves also.
The feature of the present invention that is used to solve above-mentioned problem is as follows:
(1) a kind of manufacture method of waste plastics crushed material, it is characterized in that, with waste plastics more than the softening melt temperature and do not generate fusion under the temperature of flammable decomposition gas, and then with the above shear rate in 100 (1/ seconds) carry out mixing after, cooling, solidify and make firming body, pulverize this firming body.
(2) according to the manufacture method of (1) described waste plastics crushed material, it is characterized in that softening melt temperature is 160 ℃, the temperature that does not generate flammable decomposition gas is below 270 ℃.
(3) a kind of manufacture method of waste plastics crushed material is characterized in that, with waste plastics 160~270 ℃ of following fusions, and then with the above shear rate in 100 (1/ seconds) carry out mixing after, cooling, solidify and make firming body, pulverize this firming body.
(4) according to the manufacture method of any described waste plastics crushed material in (1) to (3), it is characterized in that, use extruder to carry out fusion, mixing.
(5) according to the manufacture method of the waste plastics crushed material described in (4), it is characterized in that extruder is a double screw extruder.
(6) according to the manufacture method of any described waste plastics crushed material in (1) to (5), it is characterized in that, the fusion of waste plastics, mixing before and/or fusion, when mixing, mixed waste plastic solid particulate thing in addition carries out mixing with waste plastics.
(7) according to the manufacture method of any described waste plastics crushed material in (1) to (6), it is characterized in that, adjust the granularity of the firming body of pulverizing by sieving.
(8) a kind of ore reduction material or solid fuel are the crushed materials of being made by manufacture method any in (1) to (7).
(9) according to ore reduction material or the solid fuel described in (8), it is characterized in that, by the sieve of 0.5mm sieve mesh.
According to the present invention, set handling just can not made flammable excellent solid fuel or ore reduction material etc. with low cost with waste plastics as raw material from the equipment exhaust of waste plastics.The productivity ratio of waste plastics crushed material also improves.
In addition, the processing method of the application of the invention waste plastics can be implemented a large amount of processing of waste plastics economically.
Description of drawings
Fig. 1 is the curve map of the relation of the temperature of expression fusion waste plastics and plastics resolution ratio.
Fig. 2 is the shear rate of expression plastics and the curve map of viscosity relationship.
The specific embodiment
The waste plastics that the present invention relates to will municipal refuse, contain in the industrial waste, general discarded object etc., container package material and the heating and meltings such as waste plastics that produce at the unloading process of electrical apparatus product, automobile etc., mixing after, firming body is made in cooling, pulverizes this firming body and makes the technology of solid fuel or ore reduction material etc.As mentioned above, waste plastics is the mixture of the plastics of multiple class, and the plastics of the multiple class of melting mixing make the method for its easy fine-powdered very effective as being used to improve the grindability of waste plastics.Most of waste plastics is because sneaking into of PVC etc. contains chlorine, therefore, in the past by under the high temperature that produces chlorine with waste plastics fusion, mixing, thereby generate chlorine-containing gas, carry out removing the dechlorination processing of chlorine component thus from the waste plastics crushed material.
But, for carrying out dechlorination fully, for example in the Temperature Treatment more than 300 ℃, when then carrying out dehydrochlorination reaction, thermal decomposition, hydrolysis take place in the PET that contains in the waste plastics (PETG), paper, timber (cellulose, hemicellulose, lignin) etc., and generation is property decomposition gas (flammable organic matter) so.These flammable decomposition gases major part at normal temperatures are solids, and generally all have distillation (Sublimation) property, and therefore, the structure of capturing device becomes complicated and need carry out otherwise processed to it.And the capture thing contains the chlorine about a few percent when most, be difficult to become fuel.
Therefore, in the present invention, be the generation of the flammable decomposition gas that prevents to carry out fusion at the heating waste plastics, produce when mixing, inquired into and relevantly carried out fusion, mixing method than lower temperature.If comparing watery fusion, then exist from the chlorine of waste plastics and remove the problem that can not carry out fully, but use the low waste plastics of chlorinity, then do not carry out the dechlorination processing and just can make cl concn low waste plastics firming body, crushed material.Thereby, the preferred low waste plastics (for example, cl concn is below 2mass%) of chlorinity that uses among the present invention.In addition, the result of discussion shows the situation that allows to contain chlorine to a certain degree that exists, and it all is necessary might not handling for all situations dechlorination.For example, when finding the waste plastics crushed material used as the ore reduction material of blast furnace, because of the slag composition that is present in the stove is immobilized with the chlorine reaction, so can be according to the chlorinty omission dechlorination processing of waste plastics.In addition, even contain the cl concn height at the raw material waste plastics, containing under the high situation of cl concn of crushed material, be not to use as ore reduction material, solid fuel yet, the generation of problem such as can avoid that stove is corroded by suitably adjust the use amount in the middle of its unit interval according to containing cl concn.Thereby, the waste plastics crushed material of making even do not carry out that dechlorination is handled, so long as by fine powder is broken fully, out of question in practicality then.
On the other hand, owing to,, therefore, the grindability decline of the waste plastics firming body of manufacturing occurs, the problem that productivity ratio descends so can not get the carbonifications such as PVC after the dechlorination, the effect of embrittlement than carrying out melt process under the lower temperature.To this, find the decline of grindability to be suppressed to no problem degree by fully improving the mixing degree in waste plastics fusion, the mixing operation.Simultaneously, by carry out generation that melt process prevents flammable decomposition gas at low temperature and can be with should be as flammable decomposition gas and removed composition is also fetched as the waste plastics crushed material, therefore, also improve yield rate, improve crushed material productivity ratio on the whole.
As mentioned above, by more than the softening melt temperature and do not generate the heat treatment of carrying out waste plastics under the temperature of flammable decomposition gas, increase the solid yield after handling.At this moment, though the concentration of residual chlorine in the solid after handling is more or less high, when for example using, with the calcium reaction that is present in the blast furnace, so, also on equipment, do not cause king-sized fault even chlorine is more or less high as the reducing material of blast furnace.In addition,, should think that then the thermal discharge of firming body only increases the part of chlorine, but because as side reaction, organic matter decomposes, breaks away from, the thermal discharge of the firming body after the processing there is the tendency that diminishes if dechlorination reaction takes place.Thereby, by more than the softening melt temperature and do not generate and carry out the heat treatment of waste plastics under the temperature of flammable decomposition gas and the thermal discharge of firming body is descended.
Heating-up temperature during with waste plastics heating and melting, cooling, curing, be major premise to be warming up to the temperature that is used to remove the low-boiling compound that just contained originally and/or generated by thermal decomposition for example according to 4 of patent documentations, particularly be 150~450 ℃, more preferably 200~400 ℃, be preferably 250~380 ℃ temperature range again.In such temperature range,, produce flammable decomposition gas with hydrogen chloride by the high temperature heating.
In addition, usually handle, preferably be heated to more than 300 ℃, at this moment, need be used to handle, reclaim the equipment of the chlorine of generation for the dechlorination of carrying out plastic containing chlorine.
Thereby, be treated to the waste plastics dechlorination prerequisite with the waste plastics heating and melting after cool off and make in the equipment of firming body, need chlorine treatment facilities such as the combustion furnace of the waste plastics decomposition gas that produces in the waste plastics heating and melting operation and salt acid-restoring plant.Because such equipment cost height, institute thinks reduction Treatment of Waste Plastics cost, the temperature of the flammable decomposition gas of generation the when inventor makes firming body for fusion, mixing back cooling curing is studied, and has found relation shown in Figure 1 about the temperature of heating and melting waste plastics and the resolution ratio of plastics.Wherein, resolution ratio be with the amount (treating capacity, butt) of the waste plastics that uses in handling with handle after the ratio of yield, define with (1-yield/treating capacity) * 100 (mass%).
According to Fig. 1, the generation of waste plastics decomposition gas is considerably less till 270 ℃.Thereby by below the temperature of such generation decomposition gas, with waste plastics heating and melting, mixing, cooling curing can not need the combustion furnace five equilibrium to separate the gas treatment facility, can make the waste plastics firming body with the low-cost processes waste plastics.
If residual chlorine low concentration in the waste plastics then can not become problem during as use such as ore reduction material, solid fuels mostly the time, the low material of preferred use cl concn in the waste plastics of handling with the present invention.For example, cl concn after the waste plastics below the 2mass% is handled with the inventive method, can utilized in being blown into of blast furnace fully as the ore reduction material.
Though, under the common situation, be preferably below 270 ℃ according to the result of Fig. 1 because the kind of waste plastics does not generate some change of temperature of flammable decomposition gas.And then, if below 200 ℃, then can prevent the generation of imflammable gas more reliably.With the temperature of this situation as the maximum temperature in the resin.Maximum temperature in the resin can be measured by the conventional method that inserts thermocouple etc. in resin.And, the temperature that does not generate flammable decomposition gas is meant by heating and do not produce flammable organic temperature in fact from waste plastics, do not belong to flammable decomposition gas in this case object just like the gas that produces because of the impurity in the waste plastics (liquid gas in for example disposable igniter).
As hereinafter described, in order to carry out the mixing of waste plastics well, the following temperature that is limited to the softening fusion of waste plastics of melt temperature.Though softening melt temperature changes according to the kind of waste plastics, the main component of waste plastics is polyethylene (PE) and polypropylene (PP) usually, so preferably softening the following of melt temperature is limited to 160 ℃.If only, also can be 120 ℃ based on the waste plastics of PE.
And, because of processed waste plastics is the mixture of various plastics, be unpractiaca so descend enforcement fusion, mixing processing 160 ℃ of less thaies.That is, the plastics that carry out fusion under 160 ℃ of less thaies are mainly only PE, if handle forcibly, then the power pole-changing of mixing needs is big, simultaneously, stop up in treating apparatus sometimes, and existence is difficult to the situation that continues to handle.
Waste plastics " fusion, and then mixing " is carried out mixing when being meant the waste plastics fusion, perhaps carry out mixing with molten condition waste plastics after the fusion.At this, mixingly to carry out with the above shear rate in 100 (1/ seconds) at least.Mix by fully carrying out the mixing plastics of xenogenesis that make, high degree of dispersion increases the xenogenesis interface of plastics, thus the broken starting point of performance.If plastics with cooling curing behind such xenogenesis plastics melting mixing, then directly be cured with mutual well-mixed state between macromolecule according to its kind and the characteristic difference, but its bonding interface be not chemistry only merely physical property contact; On the other hand, the molding shrinkage of xenogenesis plastics is different because of various plastics, in the process of cooling, the xenogenesis plastics shrink with molding shrinkage separately, leave bonding interface, therefore, vacuum (vacuum voids) is had to become in inside, and when failing to form the space at the stress (residual stress) of bonding interface residual " separate does not have to separate ".The xenogenesis plastics of the high degree of dispersion bonding interface that will become is many by abundant mixing, and firming body must have very strong residual stress.Therefore, when firming body is impacted, cause that at these xenogenesis plastic bonding interfaces stress is concentrated, produce broken starting point with comparalive ease.In addition, because do not stop the factor of crevasse crack propagation, final integral becomes fragile structure, improves grindability.Outside the molding shrinkage, the difference of solubility parameter etc. also influences the raising of grindability.
Also immiscible under the most of situation of solid particulate thing beyond the waste plastics with plastics, therefore, by before fusion, mixing waste plastics, or fusion, when mixing, or fusion, mixing before and fusion, when mixing in, the solid particulate thing beyond the waste plastics is mixed in waste plastics, mixing with waste plastics, thereby become the solid particulate thing behind the cooling curing broken starting point taking place, can further improve the grindability of firming body.
As fusion, mixed method before mixing, for example use cylinder etc. in advance waste plastics and solid particulate thing to be mixed and get final product.Mixed method as fusion, when mixing can be supplied with waste plastics and solid particulate thing and mixing in device respectively to fusion, kneading device, also can supply with wherein any one earlier after, resupply another.The fusing point of solid particulate thing than the high situation of the initial melt temperature of waste plastics under, the preferred waste plastics of supplying with earlier adds shot-like particle again after the molten condition that acquires a certain degree.
As the solid particulate thing, can enumerate fossil fuels such as coal, coke, pitch, synthetic high polymers such as pure plastics, natural polymers such as starch, cellulose, their ore of metal such as iron, aluminium and iron ore, bauxite etc., inorganic matters such as mica, talcum.In addition, as the solid particulate thing, preferably use the discarded object from crops such as rice husk, tea shell, coffee shell (slag), timber, charcoal, bamboo etc. contain the so-called life entity solids such as plant of lignin.Especially be used to discarded object from crops, culled woods such as thinnings, building waste wood, also favourable from the viewpoint of earth environment protection.As mentioned above, solid particulate thing beyond the waste plastics is immiscible with plastics under most situation, therefore, become broken starting point behind, the cooling curing mixing with the waste plastics of fusion, grindability is improved, especially in the life entity solid, contain ash content, become broken starting point easily, so preferred.And, because rice husk easily becomes elongated shape, and the waste plastics of fusion can further pulverized when mixing, use effectively so can be used as broken starting point.In addition, the use level of the solid particulate thing of this situation is preferably with respect to 100 mass parts waste plastics, solid particulate thing less than 100 mass parts.Because the solid particulate thing is when to be 100 mass parts above, waste plastics is difficult to handle by efflorescence after the mixing processing.In addition, with respect to 100 mass parts waste plastics, preferred solid particulate thing is more than 5 mass parts.This is because can bring into play the additive effect of solid particulate thing better.These solid particulate things are so long as can be directed in the size for the treatment of apparatus and just can use.
The heating of waste plastics and fusion preferably use extruder to carry out on mixing one side on one side.By using extruder, can in the heating waste plastics, carry out the mixing of the above shear rate in 100 (1/ seconds) effectively.By using double screw extruder and can further improve mixing property as extruder.
The waste plastics crushed material be can make by pulverizing the waste plastics firming body of making, ore reduction material, solid fuel made.The grindability of the firming body of cooling curing is improved behind the heating and melting, can use common pulverizer to make the following fine powder of particle diameter 2mm at an easy rate.The firming body of pulverizing is preferably adjusted granularity by sieving.Can set the granularity after the pulverizing by the sieve mesh that suitably changes sieve.For example, the method for the application of the invention can obtain the fine powder of the waste plastics crushed material below the particle diameter 0.5mm by the sieve of 0.5mm sieve mesh.
Below, the order according to I. plastics, II. fusion, mixing operation, III. cooling curing operation, IV. pulverizing process illustrates an embodiment of the invention in further detail.
[I. plastics] are as the waste plastics of object of the present invention, be the raw material plastics among the present invention, can be illustrated in the waste plastics, the container package material that contain in municipal refuse, industrial waste, the general discarded object etc., and the waste plastics that in the unloading process of electrical apparatus product, automobile etc., produces etc.
Particularly, polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, haloflex, polystyrene, PETG, Merlon and nylon, other thermoplastic resins, thermosetting resin etc. are all applicable, are to use the material of the state of any two or more mixing in the above-mentioned plastics.Normally containing the plastics of chlorine to a certain degree in nature as the waste plastics of discarded object, even but do not contain the waste plastics of chloride plastics, also can use the present invention.
Answer the geomery of the plastics of heat treated, so long as the material of coarse crushing gets final product, size is that 10cm is just enough about square, for general waste plastics, there is no need to pulverize again, can handle by the former state state when being recovered, film shape, sheet, fibrous plastics also can be handled with its original shape.Can certainly fine powder broken, just the processing cost of this part uprises.
[II. fusion, mixing operation] is as fusion, mixing operation, the operation that illustration is following.That is, with waste plastics in reactor or in the extruder etc. more than 160 ℃ and the temperature of not producing imflammable gas carry out fusion.Though the temperature that does not generate flammable decomposition gas is according to the component of waste plastics and difference, be limited to 270 ℃ under the common situation.In the temperature range that does not generate flammable decomposition gas, preferably fusion under higher temperature, preferred more than 200 ℃, more preferably in the temperature range more than 230 ℃, carry out fusion, mixing.
Mixingly carry out with the above shear rate in 100 (1/ seconds) at least.Fig. 2 represents the various low density polyethylene (LDPE)s (MI: the measurement result that the pairing melt viscosity of the shear rate during melt index (Melt Index)=7,50,200) 150 ℃ changes by capillary rheometer determining.Molten plastic is a non-newtonian fluid, as shown in Figure 2, in the little zone of shear rate, the melt viscosity constant of low density polyethylene (LDPE) (LDPE).But, have the LDPE of any MI, be zone more than 100 (1/ seconds) in shear rate, viscosity descended when its shear rate increased.That is, from the viewpoint of mixing property, it is very effective that the raising of mixing reduction for mixing power, melting efficiency is carried out in the zone more than 100 (1/ seconds).
By fusion and then carry out mixing and the grindability of process in plastics thing is improved.In view of the above, though the xenogenesis plastics in the waste plastics mix mutually, they do not merge basically, do not interact each other, are easy to just become broken through very little impact after therefore solidifying, and produce broken starting point, therefore lose resistance to impact on the whole.Fusion, mixing processing can be batch (-type)s, also can be continous ways.In addition, also can be osculant such as to switch in batches.Be preferably extruder as the continous way treating apparatus, from the preferred double screw extruder of the viewpoint of mixing property.
What the processing time was suitable is 0.5 minute~30 hours.The processing time less than is in the time of 0.5 minute, and reactor temperature control is difficult, and is difficult to the Treatment of Waste Plastics thing of fusion mixing fully.In addition, treatment effeciency reduces, and is uneconomical when surpassing 30 hours the processing time.
Can make the thermophore coexistence when fusion, mixing processing.
[III. cooling curing operation] to belt cooler weight feed molten plastic, carries out cooling curing by the waste plastics after using the molten plastic carrying device with melt process.Remove heat and be after the heat treated temperature with fully solidify till temperature between entropy and processing speed calculate, for example contain under the situation of container package waste plastics, control promptly enough in the mode that cooled central part temperature becomes about 110 ℃.
In addition, when using continous way heating and melting treating apparatus, can or not cut former state ground and carry out the air cooling or drop into the medium cooling of water in the cutting of device exit.
[IV. pulverizing process] through the firming body of cooling curing operation, preferably pulverizes in the mode of the particle diameter that becomes regulation.Through the cooling curing body that the method for the invention described above obtains, i.e. the pulverizing of the pulverizing of process in plastics thing and untreated plastics specific energy is mutually carried out easily.That is,, can pulverize, for example can use jaw crusher, rotary drum grinder, ball mill, centrifugal grinder etc. as pulverizer with all types of pulverizers with the process in plastics thing that method of the present invention obtains.
Particle diameter after the pulverizing, decide according to the use order of process in plastics thing and to get final product, carry out the granularity adjustment in the mode that becomes designated size, then for example can be used as ore reduction material such as iron ore and be blast furnace etc. and make the crude fuel, the reducing material of converter of reducing material etc. of the perpendicular type stove of cast iron, the burning fuel of boiler, kiln etc., the fuel of furnace cupola, the raw material of coke oven uses.In addition, beyond the described purposes, also can be used as solid fuel and use.
Below, further specify the present invention based on embodiment.
[example 1 of the present invention] carried out fusion with double screw extruder after being crushed to general discarded object class container package waste plastics about 1cm under 180 ℃, mixing.Shear rate when mixing is 243 (1/ seconds) (the gap 0.2mm of screw diameter 31mm, screw rod and machine barrel, screw rod revolution 30rpm, shear rate π * 31 * 30/60/0.2=243).Confirm the generation of moisture (steam) from the air vent of extruder, but do not confirmed flammable decomposition gas.Its former state is carried out the air cooling, obtained the block (firming body) about about 30mm.
The blanking amount of the raw material in the time of thus and the yield of firming body have calculated the yield of firming body.In addition, the cl concn (firming body concentration of residual chlorine) in this firming body and the thermal discharge of firming body have been measured.The result is as shown in table 1.
Table 1
This firming body is carried out coarse crushing with the micromill (cutting machine) of HORAI corporate system, again the sieve by 9mm.
With this meal mince ACM pulverizer (beater grinder) with the close Krona corporate system in thin river carry out fine powder broken after, implement classification test with testing sieve, measure size distribution.The result is as shown in table 2.
Table 2
Calculated average grain diameter from size distribution.At first, to divide separately mass fraction and the substitution of sieve mesh diameter that following (1) formula (Rosin-Rammler-Bennet formula) is developed in following (2) formula that obtains by the level Four that classification test obtains, and utilize least square method to obtain proportionality constant n, the b of following formula (2).
R(Dp)=100·exp{-(Dp/De)n}…(1)
log{log[100/R(Dp)]}=n·logDp+log(b)…(2)
In above-mentioned formula (1), (2), R (Dp) is that the accumulative total of sieve mesh Dp is sieved the % that improves quality, De is particle property numerical value [R (Dp) is the numerical value of corresponding mass %], n is even numerical value (estimating the inhomogeneity index of the size distribution of powder body), b is a constant, and the index of the fine property of powder body is estimated in expression.
Calculate D50 (50% passes through screen aperture) by the n that obtains, b, calculate average grain diameter.Average grain diameter is shown in table 1 in the lump.Under 180 ℃, carry out the average grain diameter less than 500 μ m of waste plastics crushed material of the example of the present invention 1 of melt process, enough fine.
[example 2 of the present invention] will be crushed to the general discarded object class container package waste plastics of 70 mass parts about 1cm and the rice husk of 30 mass parts mixes, outside double screw extruder is supplied with, carry out the operation same, thereby made firming body and crushed material thereof with example of the present invention 1.The measurement result of the result of calculation of the measurement result of concentration of residual chlorine, firming body thermal discharge, average grain diameter and the fine powder size distribution after broken is shown in table 1, table 2 in the lump in firming body yield, the firming body.
Compare with example 1 of the present invention, the firming body yield increases, and concentration of residual chlorine descends in the firming body, and the firming body thermal discharge reduces a little.Even containing rice husk major part after processing of about 20mass% ash content, this expression still stays in the firming body.In addition, the average grain diameter after the pulverizing diminishes, and has confirmed the effect that improves grindability owing to the interpolation rice husk.
[example 3 of the present invention] will be crushed to the general discarded object class container package waste plastics and the 30 mass parts coals (trade mark: the prosperous village) mix of 70 mass parts about 1cm, outside double screw extruder is supplied with, carry out the operation same, made firming body and crushed material thereof with example of the present invention 1.The measurement result of the result of calculation of the measurement result of concentration of residual chlorine, firming body thermal discharge, average grain diameter and the fine powder size distribution after broken is shown in table 1, table 2 in the lump in firming body yield, the firming body.
Compare with example 1 of the present invention, the yield of firming body increases, and concentration of residual chlorine reduces in the firming body, and the firming body thermal discharge reduces a little.Even containing coal major part after processing of about 10mass% ash content, this expression still stays in the firming body.In addition, pulverize the back average grain diameter and diminish, confirmed the effect that improves grindability owing to the interpolation coal.Compare with example 2 of the present invention, it is littler that the average grain diameter after the pulverizing also becomes, and this is because the coal itself that adds has more good grindability than rice husk.
[comparative example 1] is made as the melting temperature of double screw extruder beyond 335 ℃, carries out and described example 1 identical operations, made firming body and crushed material thereof.Having confirmed dewaters from the air vent of double screw extruder exceptionally also discharges the exhaust that is formed by hydrogen chloride gas, organic matter.From the composition of exhaust, detected terephthalic acid (TPA).The measurement result of the result of calculation of the measurement result of concentration of residual chlorine, firming body thermal discharge, average grain diameter and the fine powder size distribution after broken is shown in table 1, table 2 in the lump in firming body yield, the firming body.
Fully reduced concentration of residual chlorine in the firming body in the comparative example 1.In addition, average grain diameter is little, and by fine-powdered, its main cause is the ratio height of the following superfine powder of 75 μ m.In addition, the following superfine powder of this 75 μ m has the problem points on the safety such as dust explosion, need charge into the reply cost of equipment of nitrogen etc.
Shear rate when [comparative example 2] is will be with double screw extruder mixing is made as 81 (1/ seconds) (screw rod revolution 10rpm) in addition, carries out and the invention described above example 1 identical operations, has implemented classification test.The measurement result of the result of calculation of the measurement result of concentration of residual chlorine, firming body thermal discharge, average grain diameter and the fine powder size distribution after broken is shown in table 1, table 2 in the lump in firming body yield, the firming body.
Compare with example 1 of the present invention, the shear rate when mixing is in the comparative example 2 beyond the scope of the invention, and obviously average grain diameter is big, not by fine-powdered.
[comparative example 3] will utilize the mixing temperature of double screw extruder to be made as beyond 335 ℃, carry out the operation same with the invention described above example 2, implement classification test.Having confirmed dewaters from the air vent of double screw extruder exceptionally also discharges the exhaust that is formed by hydrogen chloride gas, organic matter.Detected terephthalic acid (TPA) in the composition of exhaust.The measurement result of the result of calculation of the measurement result of concentration of residual chlorine, firming body thermal discharge, average grain diameter and the fine powder size distribution after broken is shown in table 1, table 2 in the lump in firming body yield, the firming body.
Average grain diameter is little in the comparative example 3, and by fine-powdered, its main cause is the ratio height of the following micropowders of 75 μ m.In addition, the following superfine powder of this 75 μ m has the problem points on the safety such as dust explosion, need charge into the reply cost of equipment of nitrogen etc.
Treatment temperature when [comparative example 4] will utilize double screw extruder mixing is made as beyond 140 ℃, has attempted the processing same with example of the present invention 1.But screw-rod engine stops because of excess load when beginning to handle back about 5 minutes, fails to continue to handle.After the double screw extruder cooling, when extracting screw rod, the inner waste plastics solid that not fusion is arranged that stops up.
From above result as can be known, in the example 1~3 of the present invention, although carry out fusion, mixing at low temperature, all crushed materials all carefully are crushed to below the particle mean size 500 μ m.By adding rice husk, coal, further improved grindability.Example 1 relatively more of the present invention and comparative example 1, in the example 1 then of the present invention in the firming body concentration of residual chlorine do not descend and the firming body yield increases, the thermal discharge of firming body also increases simultaneously.Can clearly improve the productivity ratio of crushed material in view of the above.Think this be since comparative example 1 in the dechlorination process terephthalic acid (TPA) as combusting component also break away from, and in example of the present invention combusting component with residual.
On the other hand, with comparative example 3, compare with comparative example 1, though then added rice husk, average grain diameter still becomes greatly, at first sight seems that grindability is descending.But though a little change of average grain diameter is big in the comparative example 3, according to table 2, comparative example 3 is than the ratio height of comparative example 1 its 150~500 μ m, 75~150 μ m particle diameters, and the amplitude of particle-size distribution is narrow, and grindability is improved.Therefore, can confirm by adding rice husk the effect that plays " showing better grindability " by forming broken starting point.
Claims (9)
1. the manufacture method of a waste plastics crushed material, it is characterized in that, with waste plastics more than the softening melt temperature and do not generate fusion under the temperature of flammable decomposition gas, and then with the above shear rate in 100 (1/ seconds) carry out mixing after, cooling, solidify and make firming body, pulverize this firming body.
2. the manufacture method of waste plastics crushed material according to claim 1 is characterized in that, softening melt temperature is 160 ℃, and the temperature that does not generate flammable decomposition gas is below 270 ℃.
3. the manufacture method of a waste plastics crushed material is characterized in that, with waste plastics 160~270 ℃ of following fusions, and then with the above shear rate in 100 (1/ seconds) carry out mixing after, cooling, solidify and make firming body, pulverize this firming body.
4. according to the manufacture method of any described waste plastics crushed material in the claim 1 to 3, it is characterized in that, use extruder to carry out fusion, mixing.
5. according to the manufacture method of the waste plastics crushed material described in the claim 4, it is characterized in that extruder is a double screw extruder.
6. according to the manufacture method of any described waste plastics crushed material in the claim 1 to 5, it is characterized in that, the fusion of waste plastics, mixing before and/or fusion, when mixing, the solid particulate thing beyond the mixed waste plastic carries out mixing with waste plastics.
7. according to the manufacture method of any described waste plastics crushed material in the claim 1 to 6, it is characterized in that, adjust the granularity of the firming body of pulverizing by sieving.
8. ore reduction material or solid fuel are the crushed materials of being made by manufacture method any in the claim 1 to 7.
9. ore reduction material according to claim 8 or solid fuel is characterized in that, by the sieve of 0.5mm sieve mesh.
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CN105647611A (en) * | 2014-11-14 | 2016-06-08 | 何湘贤 | Fuel extractive |
CN112771742A (en) * | 2018-10-19 | 2021-05-07 | 三菱综合材料株式会社 | Method for processing coated electric wire |
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JP4775485B2 (en) | 2011-09-21 |
KR101134809B1 (en) | 2012-04-13 |
CN102149526B (en) | 2013-11-20 |
KR20110036771A (en) | 2011-04-08 |
WO2010030038A1 (en) | 2010-03-18 |
JP2010089500A (en) | 2010-04-22 |
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