CN109790979A - The processing method of carbonaceous refuse - Google Patents
The processing method of carbonaceous refuse Download PDFInfo
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- CN109790979A CN109790979A CN201780059424.7A CN201780059424A CN109790979A CN 109790979 A CN109790979 A CN 109790979A CN 201780059424 A CN201780059424 A CN 201780059424A CN 109790979 A CN109790979 A CN 109790979A
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- Prior art keywords
- carbonaceous refuse
- ozone
- refuse
- carbonaceous
- surfactant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Abstract
A kind of processing method of carbonaceous refuse is provided.It can make carbonaceous refuse full combustion by less labour using the processing method.After contacting carbonaceous refuse with the combination of surfactant and hydrogen peroxide as processing promotor or ozone, the carbonaceous refuse is burned.
Description
[technical field]
The present invention relates to a kind of by carbonaceous refuse, the side that the waste plastics especially containing carbon fiber burns to be handled
Method.
[background technique]
In recent years, the structural material as lightweight and high intensity, is formed by the basis materials such as resin or metal and carbide
The demand of composite material sharply increasing.Especially it is compounded with the matrix material being made of thermosetting resin or thermoplastic resin
The increase of the demand of the carbon fibre reinforced plastic (CFRP:Carbon Fiber reinforced plastics) of material and carbon fiber
It is very significant.
On the other hand, with the increase of the demand, headed by the waste plastics containing carbon fiber, BOF (Biomass oil
fuel)、ASR(Automobile shredder residue)、RPF(Refuse derived paper and plastics
Densified fuel), RDF (Refuse derived fuel), sawdust, damaged tire, rubber scrap, water absorbent polymer
Waste, municipal refuse, the waste of thermosetting property and thermoplastic resin, discarded FRP (Fiber reinforced
Plastics), the waste containing carbide such as waste of carbon fiber waste, optical fiber waste, solar battery is useless
Abandoning amount is also increasing.
As the processing method of this carbonaceous refuse, there is one kind and make carbonaceous refuse etc. in cement production process
For the method for carrying out burning disposal while alternative fuel effective use.
However, when burning disposal carbonaceous refuse, it is carbon containing discarded in the case where carbonaceous refuse has anti-flammability etc.
Carbide contained in object can generate combustion residue, and the carbide of the combustion residue may be mixed into exhaust.Accordingly, there exist rows
The failure as caused by carbide attached thereto may occur for the dust-collecting equipment (electric precipitator, bag filter etc.) of gas
The problem of (electric short circuit accident, damage of filter etc.).
As the method for avoiding this problem, have a kind of before the processing for carrying out cement production process, carries out carbon fiber
The method for the processing that equal carbide are removed from carbonaceous refuse, but it is extremely complex for carrying out pretreatment.
Therefore, as the processing method for removing the processing of carbide in advance can be omitted, a kind of crushing carbonaceous waste is proposed
After gurry makes its average grain diameter 3mm or less, which, which is supplied to the internal temperature in cement kiln, is
The method of 1200 DEG C or more of position (for example, referring to patent document 1).
[existing technical literature]
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-131463 bulletin
[summary of the invention]
Subject to be solved by the invention
It needs high-intensitive carbonaceous refuse fine crushing however, existing in method described in patent document 1 to averagely
Partial size is 3mm nano sized particles below, and in order to crush the problem of needing a large amount of labours.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide one kind to make to contain by less labour
The processing method of the clean-burning carbonaceous refuse of carbide contained in carbon waste.
Means for solving the problems
To achieve the goals above, the processing method of carbonaceous refuse of the invention is a kind of containing for burning carbonaceous refuse
The processing method of carbon waste, it is characterised in that: promote the carbonaceous refuse with the processing containing following (1) or following (2)
Into after agent contact, the carbonaceous refuse is burned,
(1) surfactant and hydrogen peroxide,
(2) ozone.
In the processing method of carbonaceous refuse of the invention, surfactant and hydrogen peroxide (H are being used2O2) conduct
When the processing promotor, improve the wetability of carbonaceous refuse by surfactant, thus hydrogen peroxide can with it is carbon containing
Waste comes into full contact with.Moreover, carbide contained in oxygen contained in hydrogen peroxide and carbonaceous refuse is efficient when burning
Ground reaction, therefore can sufficiently improve the flammability of carbonaceous refuse.In addition, hydrogen peroxide in the present invention can be speculated to carbonization
The combustible improvement of object is to be supplied to the hydrogen peroxide of burning disposal equipment (for example, the burning facilities such as cement kiln) in phase
To lower temperature range internal disintegration and active oxygen radical is released, which promotes the combustion reaction of carbide
And the effect generated.
On the other hand, it can speculate when using ozone as the processing promotor, pass through the table of ozone and carbonaceous refuse
The contact such as inner surface of internal voids possessed by face or carbonaceous refuse (hole), generates and carbon-in carbonaceous refuse
The ozone-induced cracking phenomenon that crack is generated in the ozone oxidation phenomenon or organic polymer of carbon double bond oxicracking is same or similar
Phenomenon, to improve the flammability of the carbonaceous refuse.As a result, when burning, the burning of carbide contained in carbonaceous refuse
Property is improved, therefore can sufficiently improve the flammability of carbonaceous refuse.
Therefore, the processing method of carbonaceous refuse according to the present invention, due to not needing the removal of progress carbide in advance,
In addition it is also possible to the average grain diameter of carbonaceous refuse is not made to be reduced to such as 3mm very small dimensions below, thus can by compared with
Few labour makes carbide full combustion contained in carbonaceous refuse.
In the processing method of carbonaceous refuse of the invention, use surfactant and hydrogen peroxide as the processing
When promotor, the processing promotor includes (1) surfactant and hydrogen peroxide, it is preferable that is made described carbon containing discarded
Object and surfactant fluid and reduce partial size, after further contacting it with hydrogen peroxide on this basis, burn this and contain
Carbon waste.
According in this respect, due to reducing carbonaceous refuse partial size and contacting it with hydrogen peroxide, further mention
High combustible improvement.Further, since making carbonaceous refuse and surfactant fluid and reducing partial size, therefore can
By the surfactant, when the partial size of carbonaceous refuse being inhibited to reduce or the partial size of carbonaceous refuse reduce after dust production
It is raw.
In the processing method of carbonaceous refuse of the invention, use surfactant and hydrogen peroxide as the processing
When promotor, the processing promotor includes (1) surfactant and hydrogen peroxide, it is preferable that when described carbon containing discarded
When the amount of object is 100 mass parts, the amount of the hydrogen peroxide be 15 mass parts or more and 100 below the mass.When carbon containing discarded
When the amount of object is 100 mass parts, if the amount of hydrogen peroxide less than 15 mass parts, may be unable to fully obtain carbonaceous refuse
Combustible improvement.On the other hand, from the viewpoint of the flammability for improving carbonaceous refuse, for the amount of hydrogen peroxide
The upper limit there is no limit.However, from the viewpoint of reagent cost etc., when the amount of carbonaceous refuse is 100 mass parts, if mistake
The amount of hydrogen oxide is more than 100 mass parts, then cost will increase, therefore be not preferred.
In the processing method of carbonaceous refuse of the invention, use surfactant and hydrogen peroxide as the processing
When promotor, the processing promotor includes (1) surfactant and hydrogen peroxide, it is preferable that when the hydrogen peroxide
Amount when being 100 mass parts, the amount of the surfactant be 0.01 mass parts or more and 25 below the mass.Work as hydrogen peroxide
Amount when being 100 mass parts, if the amount of surfactant less than 0.01 mass parts, may be unable to fully obtain carbonaceous refuse
Combustible improvement.On the other hand, from the viewpoint of the flammability for improving carbonaceous refuse, for surfactant
Amount the upper limit there is no limit.However, from the viewpoint of reagent cost etc., when the amount of hydrogen peroxide is 100 mass parts, if
The amount of surfactant is more than 25 mass parts, then cost will increase, therefore be not preferred.
In the processing method of carbonaceous refuse of the invention, when using ozone as the processing promotor, the place
Managing promotor includes described (2) ozone, it is preferable that makes the ozone with ozone concentration 100ppm or more and 6000ppm or less
Gas form contacted with the carbonaceous refuse.If the ozone concentration of gas form is less than 100ppm, may be unable to fully
Obtain the combustible improvement of carbonaceous refuse.On the other hand, from the viewpoint of the flammability for improving carbonaceous refuse,
For ozone concentration the upper limit there is no limit.However, from the viewpoint of cost for generating ozone etc., when gas form
When ozone concentration is more than 6000ppm, cost be will increase, therefore be not preferred.
In the processing method of carbonaceous refuse of the invention, when using ozone as the processing promotor, the place
Managing promotor includes described (2) ozone, it is preferable that makes the ozone with ozone concentration 1ppm or more and 50ppm liquid below
Volume morphing is contacted with the carbonaceous refuse.If the ozone concentration of liquid form is less than 1ppm, may be unable to fully be contained
The combustible improvement of carbon waste.On the other hand, with above-mentioned gas form the case where, is identical, from improvement carbonaceous refuse
Flammability from the viewpoint of, for ozone concentration the upper limit there is no limit.However, from the sight of cost for generating ozone etc.
From the point of view of point, when the ozone concentration of liquid form is more than 50ppm, cost be will increase, therefore is not preferred.
In the processing method of carbonaceous refuse of the invention, when using ozone as the processing promotor, the place
Managing promotor includes described (2) ozone, it is preferable that make the carbonaceous refuse further with surfactant fluid.As a result, by
In the wetability for improving carbonaceous refuse by surfactant, therefore, ozone is especially the case where its form is liquid
Under, it can be come into full contact with carbonaceous refuse.Thereby, it is possible to obtain more good combustible improvement.
In the processing method of carbonaceous refuse of the invention, when using ozone as the processing promotor, the place
Managing promotor includes described (2) ozone, it is preferable that and make the carbonaceous refuse and surfactant fluid and reduces partial size,
After further contacting it with ozone on the basis of this, the carbonaceous refuse is burned.As a result, due to making the partial size of carbonaceous refuse
Reduce and contact it with ozone, therefore further improves combustible improvement.Further, since make carbonaceous refuse with
Surfactant fluid and reduce partial size, therefore by the surfactant, can inhibit carbonaceous refuse partial size reduce when
Or carbonaceous refuse partial size reduce after dust generation.
In addition, in the processing method of carbonaceous refuse of the invention, it is preferable that the average grain diameter of the carbonaceous refuse
For 10mm or less.Combustible improvement can be obtained not reducing the average grain diameter of carbonaceous refuse greatly, but
If average grain diameter is decreased to 10mm or so, effect be will increase.
In addition, in the processing method of carbonaceous refuse of the invention, it is preferable that the carbonaceous refuse is selected from carbon fiber
The waste for tieing up reinforced plastics (CFRP:Carbon Fiber reinforced plastics) is (hereinafter referred to as " discarded
CFRP”)、BOF(Biomass oil fuel)、ASR(Automobile shredder residue)、RPF(Refuse
Derived paper and plastics densified fuel), RDF (Refuse derived fuel), sawdust, useless wheel
Tire, rubber scrap, the waste of water absorbent polymer, municipal refuse, the waste of thermosetting property and thermoplastic resin, discarded FRP
The waste of (Fiber reinforced plastics), carbon fiber waste, optical fiber waste and solar battery forms
One of group or a variety of wastes.Due to containing carbide in these wastes, it is to be processed in these wastes
When object, processing can be effectively performed by the above method.
In addition, in the processing method of carbonaceous refuse of the invention, it is preferable that the carbonaceous refuse contains carbon fiber
Dimension.According to the present invention, if object to be processed is the waste containing carbide, burning facilitation effect can be obtained, but work as carbon
When compound is carbon fiber, extra high burning facilitation effect can be obtained.
In addition, the carbonaceous refuse and the place can also be made in the processing method of carbonaceous refuse of the invention
After managing promotor (combination of surfactant and hydrogen peroxide or ozone) contact, it is carbon containing that this is burned in cement manufacture plant
Waste.
[simple declaration of attached drawing]
Fig. 1 is indicated in test example 1, the result of thermogravimetric amount measurement test when carbonaceous refuse is discarded CFRP
Figure, the longitudinal axis indicate that the weight reduction rates (quality %) of sample, horizontal axis indicate heating temperature (DEG C).
Fig. 2 is indicated in test example 1, the figure of the result of thermogravimetric amount measurement test when carbonaceous refuse is damaged tire,
The longitudinal axis indicates that the weight reduction rates (quality %) of sample, horizontal axis indicate heating temperature (DEG C).
Fig. 3 is indicated in test example 3, the result of thermogravimetric amount measurement test when carbonaceous refuse is discarded CFRP
Figure, the longitudinal axis indicate that the weight reduction rates (quality %) of sample, horizontal axis indicate heating temperature (DEG C).
Fig. 4 is indicated in test example 4, the figure of the result of thermogravimetric amount measurement test when carbonaceous refuse is damaged tire,
The longitudinal axis indicates that the weight reduction rates (quality %) of sample, horizontal axis indicate heating temperature (DEG C).
[specific embodiment]
The present invention relates to a kind of by carbonaceous refuse burning come the processing method of the carbonaceous refuse handled.
As the object to be processed, as long as the waste containing carbide, is not particularly limited, specifically, such as
Discarded CFRP, BOF, ASR, RPF, RDF, sawdust, damaged tire, rubber scrap, the waste of water absorbent polymer, city can be enumerated
Rubbish, the waste of thermosetting property and thermoplastic resin, discarded FRP, carbon fiber waste, optical fiber waste, solar battery
Waste etc..Can be using a kind of waste as object to be processed, or it can also be using two or more wastes as to be processed
Object.
In processing method of the invention, contact above-mentioned object to be processed i.e. carbonaceous refuse with processing promotor.Moreover,
The combination for using surfactant and hydrogen peroxide or ozone are as the processing promotor.
As surfactant, as long as being the various surfactants selected from anionic species, nonionic class and cationic
One of or it is a variety of, in particular it is preferred to use the surfactant of anionic species or nonionic class.
As the surfactant of anionic species, such as alkyl ether sulphate sodium, alkyl sulfate sodium, straight chain alkane can be enumerated
Base benzene sulfonic acid sodium salt (LAS), sodium soap, fatty acid potassium, alpha-sulfo fatty acid ester sodium, alpha-olefin sodium sulfonate, sodium alkyl sulfonate etc..
In addition, the surfactant as nonionic class, such as sucrose fatty ester, sorbitan-fatty can be enumerated
Acid esters, polyoxyethylene sorbitan fatty acid esters, Marlamid, polyoxyethylene alkyl ether, polyoxyethylene alkane
Base phenyl ether etc..
When the amount of carbonaceous refuse is 100 mass parts, the amount of surfactant be 0.1 mass parts or more, 10 mass parts with
Under, more than preferably 0.5 mass parts 6 below the mass, and more than more preferably 1 mass parts 3 below the mass.
In addition, the amount of surfactant is 0.01 mass parts or more, 25 mass when the amount of hydrogen peroxide is 100 mass parts
Part hereinafter, more than preferably 0.2 mass parts 20 below the mass, more than more preferably 0.3 mass parts 15 below the mass.
The lower limit of amount about surfactant may be unable to fully obtain carbonaceous waste if its amount is less than above range
The combustible improvement of gurry.
From improve carbonaceous refuse flammability from the viewpoint of, for surfactant amount the upper limit there is no limit.
However, from the viewpoint of reagent cost etc., even if addition is more than the surfactant of above range, it is also difficult to acquisition and surface
The corresponding improvement of the usage amount of activating agent, and cost will increase, therefore be not preferred.
The purity etc. of hydrogen peroxide is not particularly limited, and is using the usually available hydrogen peroxide such as 30% aqueous solution
It can.
When the amount of carbonaceous refuse is 100 mass parts, the amount of hydrogen peroxide is 15 mass parts or more, preferably 30 mass
Part or more, it is more than more preferably 45 mass parts.
The lower limit of amount about hydrogen peroxide, when the amount of carbonaceous refuse is 100 mass parts, if the amount of hydrogen peroxide is small
In 15 mass parts, then may be unable to fully obtain the combustible improvement of carbonaceous refuse.
From improve carbonaceous refuse flammability from the viewpoint of, for hydrogen peroxide amount the upper limit there is no limit.So
And from the viewpoint of reagent cost etc., when the amount of carbonaceous refuse is 100 mass parts, if the amount of hydrogen peroxide is more than 100
Mass parts, then cost will increase, therefore be not preferred.
In processing method of the invention, the combination of surfactant and hydrogen peroxide is being used to promote as above-mentioned processing
When agent, the method for contacting it with above-mentioned carbonaceous refuse is not particularly limited.As long as that is, making surfactant and peroxidating
Hydrogen acts on carbonaceous refuse.Specifically, as long as example, carrying out surfactant and/or peroxidating to carbonaceous refuse
The dropwise addition of hydrogen, spraying, coating etc. such as also can according to need, while being mixed, being stirred at the operation.Alternatively, can also incite somebody to action
Carbonaceous refuse is impregnated into the solution containing surfactant and/or hydrogen peroxide, or as needed, and it is carbon containing discarded to shake this
It is impregnated while object.Alternatively, carbonaceous refuse can also be stood to and is exposed to surfactant and/or hydrogen peroxide vapour
In the environment changed, or as needed, it is exposed to while shaking the carbonaceous refuse in the environment.More typically,
Such as it is also possible to that the environment of the thermal decomposition of hydrogen peroxide occurs around carbonaceous refuse in the Inner Constitution of burning facility
Method etc..
Surfactant and hydrogen peroxide can use under admixture, also can be used alone.Under admixture
When using the two, mixed method is not particularly limited, as long as the common method of liquid mixed method, can be any
Method.For example, being mixed by stirring i.e. after the surfactant of addition predetermined amount into mixed proportion higher hydrogen peroxide
It can.In addition it is also possible to prepare simultaneously containing both aqueous solution come using.On the other hand, it can also live surface is used alone
When property agent or hydrogen peroxide, prepare respectively respective aqueous solution come using.But in aqueous solution of the preparation containing surfactant
When, from the viewpoint of the viscosity for never increasing the aqueous solution, it is preferable that add 0.1 mass parts into the water of 100 mass parts to 30
The surfactant of mass parts prepares aqueous solution, it is highly preferred that 1 mass parts of addition are made to the surfactant of 10 mass parts
Standby aqueous solution.
In addition, the time for contacting surfactant and hydrogen peroxide with carbonaceous refuse is not particularly limited.That is,
For example, can also can also thrown while investment before carbonaceous refuse to be put into the equipment for being used for burning
After entering.In addition to this, surfactant is being used alone or when hydrogen peroxide, for make that it contacts with carbonaceous refuse when
Between be also not particularly limited.I.e., it is possible to contact surfactant before hydrogen peroxide with carbonaceous refuse, it can also be simultaneously
Contact, can also be such that surfactant contacts after hydrogen peroxide with carbonaceous refuse.But it is filled from carbonaceous refuse is assigned
From the viewpoint of the wettability divided, it is preferable that contact surfactant before hydrogen peroxide with carbonaceous refuse.
On the other hand, in other aspects of the present invention, make carbonaceous refuse and surfactant fluid and reduce partial size,
Further contact it with hydrogen peroxide on this basis.Reduced as a result, by the partial size, further improves combustible change
Kind effect.In addition, when the partial size of carbonaceous refuse being inhibited to reduce or the partial size of carbonaceous refuse reduces by surfactant
The generation of dust afterwards.
It is not special for the time for contacting surfactant and hydrogen peroxide with carbonaceous refuse in above-mentioned aspect
Limitation.That is, for example, can also be gone back while investment before carbonaceous refuse to be put into the equipment for being used for burning
It can be after investment.More specifically, for example, it may be surfactant and mistake is added dropwise in the carbonaceous refuse after reducing to partial size
Carbonaceous refuse after hydrogen oxide, or after partial size is reduced is impregnated into containing after in surfactant and hydrogenperoxide steam generator, or
After hydrogen peroxide is added dropwise in carbonaceous refuse after reducing after from dropwise addition surfactant to partial size, or by grain after dropwise addition surfactant
After carbonaceous refuse after diameter reduction is impregnated into hydrogen peroxide, the method in burning facility is put into, is also possible to
When carbonaceous refuse after partial size is reduced is put into burning facility or after investment, surfactant and hydrogen peroxide are sprayed
Mist makes them in the interior contact of burning facility to the inside of burning facility, or reduces partial size after surfactant is added dropwise
After carbonaceous refuse afterwards puts into burning facility, hydrogen peroxide is sprayed to the inside of burning facility, and is burning them
The method etc. of the interior contact of equipment.
On the other hand, in processing method of the invention, when using ozone as above-mentioned processing promotor, to make its with
The method of above-mentioned carbonaceous refuse contact is not particularly limited.As long as that is, can have ozone around carbonaceous refuse
Method.Therefore, ozone can be made to contact under gas form, ozone can also be made to connect therewith under liquid form
Touching.Specifically, such as can enumerate in closed container method carbonaceous refuse being exposed in the gas containing ozone, or
Person, the method etc. carbonaceous refuse being impregnated into the solution containing ozone.
For example, in the method being exposed in closed container in ozone, it is preferable that in ozone concentration be 100ppm or more
Exposure 1 hour or more in environment, it is highly preferred that exposure 3 hours or more in the environment that ozone concentration is 500ppm or more.This
Outside, for example, in the method being impregnated into the solution containing ozone, it is preferable that in the solution that ozone concentration is 1ppm or more
Dipping 1 hour or more, it is highly preferred that being impregnated 1 hour or more in the solution that ozone concentration is 10ppm or more.In addition, will be smelly
Oxygen is dissolved in solvent in use, from the viewpoint of being easily handled, it is preferable that the solvent is water.I.e., it is preferable to use ozone
Water.
Ozone, for example, using by have JISB9946 " waste water and with water ozone treatment apparatus-specification items and ozone it is dense
The ozone that the ozone generating apparatus for the specification recorded in degree measuring method " obtains.Specifically, for example, oxygen can be passed through
Inspissator is after the oxygen that separation of nitrogen in unstrpped gas, that is, air generates that purity is 90% or more, using in ozone generator
The ozone for converting ozone for the oxygen and obtaining.
When the ozone yield (mg/ hours) of ozone generating apparatus is converted into environmental gas concentration, use is below
Formula (1),
Ozone concentration (ppm)=ozone generating apparatus ozone yield (mg/ hours)/gas in environment is in closed appearance
Existing spatial volume (m in device3)/2.14…(1)。
The preparation method of solution containing ozone can enumerate the ozone that will be generated in ozone generating apparatus, and to be dissolved into water etc. molten
Dissolved under pressure method, bubble-free gas dissolution method, gas bubble method, diaphragm dissolution method, filled layer dissolution method in agent etc..In addition,
It is also possible to not need direct electrolysis method of ozone generating apparatus etc..Wherein, from the viewpoint of the Ozone Water for obtaining high concentration,
It is preferred that dissolved under pressure method, bubble-free gas dissolution method.
In addition, when using solution containing ozone, it is preferable that make to contain surfactant in the solution, or by table
Face activating agent is coated in advance or is sprayed in carbonaceous refuse, the wettability of Lai Gaishan carbonaceous refuse.Thereby, it is possible to obtain more
Add good combustible improvement.As described above, as the surfactant, as long as selected from anionic species, nonionic
One of various surfactants of class or cationic are a variety of, wherein preferably anionic species and nonionic class two
One of kind surfactant is a variety of.For example, anionic based surfactants can enumerate alkyl ether sulphate sodium, alkyl sulfide
Acid esters sodium, sodium n-alkylbenzenesulfonate (LAS), sodium soap etc., rather than ionic species surfactant can then enumerate sucrose fat
Acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Marlamid etc..
On the other hand, in other aspects of the present invention, carbonaceous refuse can be made to reduce with surfactant fluid
Partial size further contacts it with ozone on this basis.Reduced as a result, by the partial size, is further improved combustible
Improvement.In addition, when the partial size of carbonaceous refuse being inhibited to reduce or the partial size of carbonaceous refuse subtracts by surfactant
The generation of dust after small.
In this case, when the amount of carbonaceous refuse is 100 mass parts, the amount of surfactant is 0.1 mass parts
Above 10 below the mass, and more than preferably 0.5 mass parts 6 below the mass, more than more preferably 1 mass parts 3 mass parts with
Under.
In addition, carrying out the amount in use, the liquid when dissolved ozone containing surfactant in making the solution containing ozone
When for 100 mass parts, it is preferable that more than 0.01 mass parts of amount for the surfactant for containing it 1 below the mass.Work as table
When the usage amount of face activating agent is less than 0.01 mass parts, the carbonaceous refuse containing high hydrophobicity carbide may be unable to improve
Wettability possibly can not obtain the improvement of wettability corresponding with the usage amount of surfactant furthermore when being greater than 1 mass parts
Effect.
Hereinafter, being discarded CFRP or damaged tire with object to be processed, returned to carry out heat to the object to be processed in cement kiln
Receive or chemical recovery and in case where carrying out processing of the invention, illustrate carbonaceous refuse of the invention in further detail
Processing method.
It is illustrated firstly, treating the i.e. discarded CFRP of processed material.Carbon fibre reinforced plastic (CFRP:Carbon Fiber
Reinforced plastics) it is lightweight and the very excellent structural material of mechanical performance, corrosion resistance.Carbon fiber contains
Rate is generally 30 mass % to 80 mass % or so.The containing ratio of the carbon fiber of CFRP can be by according to JISK7075 " carbon fiber
The test method of the fiber containing ratio and voidage test method of dimension reinforced plastics " is found out.
As carbon fiber used in CFRP, using being formed by graphite-like carbon and the excellent fibers of mechanical performances such as rigidity.
Specifically, as carbon fiber, for example, in addition to by polypropylene nitrile, pitch class or cellulosic fibre etc. in oxidative environment
After being heated to 150 DEG C to 400 DEG C progress flame-resistant process, carbonization or stone are carried out at 300 DEG C to 2500 DEG C in inert environments
Outside carbon fiber obtained from blackization processing, the activated carbon fibre etc. activated in the semiactives environment such as vapor can also be enumerated.
As basis material used in CFRP, thermoplastic resin or thermosetting resin are used.Specifically, as thermoplasticity
Resin, such as polyamide or acrylic resin, nylon resin etc. can be enumerated.In addition, as thermosetting resin, such as
Epoxy resin, unsaturated polyester resin, polyimide resin, bimaleimide resin, phenolic resin etc. can be enumerated.
Then, damaged tire is illustrated.In the material composition of tire, primary raw material is taken turns with for the large-scale of truck etc.
Synthetic rubber (SBR, the styrene-of natural rubber (the cis- Isosorbide-5-Nitrae-polyisoprene) and the small tyre for car etc. of tire
Butadiene random copolymer) difference is very big, and rubber is 40 mass % to 60 mass %, and the compounding agents such as carbon black, sulphur are 20 matter
% to 40 mass % is measured, the tyre cord being made of steel and textile is 10 mass % to 20 mass %, and steel bead wire is 3 matter
Measure % to 10 mass %.
In the present embodiment, firstly, will be made of into above-mentioned in the disintegrating apparatus such as rotary-cut blade shearing Roughpulverizer
After dividing the i.e. discarded CFRP of the waste of the CFRP constituted or damaged tire coarse powder to be broken to 50mm or less, pass through jaw crusher, roller is ground
Its partial size is decreased to predetermined size by the disintegrating apparatus such as machine, roller press, crusher.In addition, containing more combustion for damaged tire etc.
The waste of the good ingredient of burning property, can be broken to the 50mm stage below in coarse powder terminates to crush.In addition, in order to efficiently into
The comminution process of the harder wastes such as the discarded CFRP of row, is arranged the grading plants such as partition preferably in the disintegrating apparatus of back segment.
In addition, need the partial size of overspending labour to reduce in processing method of the invention and be not required, but in order to
It is efficiently handled, it is preferable that a certain extent reduce the partial size of discarded CFRP or damaged tire.Specifically, it is handling
It is 10mm hereinafter, preferably 7mm or less in the case where discarded CFRP.In the case where handling waste tire, be 50mm hereinafter,
Preferably 30mm or less.
Here, the average grain diameter of the partial size discarded CFRP that reduces that treated or damaged tire can be by using JISZ8801
The discarded CFRP dry after handling partial size reduction of sieve specified in " testing screen (sieve)-first part: wire-mesh screen " or useless wheel
Tire is sieved, and is calculated the partial size for being equivalent to 50 mass % of the sample remained on sieve and found out.
Hereinafter, to the mode for contacting partial size reduce that treated discarded CFRP or damaged tire with above-mentioned processing promotor,
It is divided into and uses the case where combination of surfactant and hydrogen peroxide is as the processing promotor and use ozone as the processing
The case where promotor, illustrates in further detail.
(1) combination of surfactant and hydrogen peroxide
As described above, as make partial size reduce after discarded CFRP or damaged tire contact with surfactant and hydrogen peroxide
Method, for occur around discarded CFRP or damaged tire in the Inner Constitution of cement kiln hydrogen peroxide thermal decomposition environment
Method etc..It is further possible to be that surface is lived during after the partial size of discarded CFRP or damaged tire reduce
Property agent be added drop-wise to after discarded CFRP or damaged tire and reduce partial size come after obtaining discarded CFRP or damaged tire containing surfactant,
The method for contacting discarded CFRP or damaged tire containing the surfactant with hydrogen peroxide.
Specifically, for example, it may be surfactant and peroxide is added dropwise in discarded CFRP or damaged tire after reducing to partial size
After discarded CFRP or damaged tire after changing hydrogen, or after partial size is reduced are impregnated into surfactant and hydrogen peroxide, or it is added dropwise
After hydrogen peroxide is added dropwise in discarded CFRP from surfactant to partial size or damaged tire after reducing after, or will after dropwise addition surfactant
After discarded CFRP or damaged tire after partial size reduction are impregnated into hydrogen peroxide, the method in cement kiln is put into, it can also
To be in the discarded CFRP after reducing partial size or after damaged tire puts into cement kiln, or by surfactant and hydrogen peroxide
It is sprayed to the inside of cement kiln, and makes them in the interior contact of cement kiln, or after being added dropwise after surfactant and reducing partial size
Discarded CFRP or partial size reduce after tire put into burning facility after, hydrogen peroxide is sprayed in burning facility
Portion, and make them in method of the interior contact of burning facility etc..CFRP is discarded in cement kiln or the investment position of damaged tire does not have
Have and particularly limit, can on front side of the kiln (kiln burner side), kiln tail side or calcining furnace etc. it is any from put into.
But since the boiling point of hydrogen peroxide is 141 DEG C (purity 90%), hydrogen peroxide can be stood after putting into cement kiln
It thermally decomposes, therefore in order to efficiently utilize hydrogen peroxide to combustible improvement, makes using in the inside of cement kiln
When its method contacted, it is preferable that by discarded CFRP or damaged tire and surfactant and hydrogen peroxide from identical or very connect
Close position is substantially simultaneously put into cement kiln simultaneously.
Specifically, for example, being arranged the first inflatable mouth of discarded CFRP or damaged tire in kiln burner etc., and with this
Surfactant and hydrogen peroxide is arranged in the adjacent mode of one inflatable mouth, or only the second inflatable mouth of hydrogen peroxide.
Finally, in the inside of cement kiln by discarded CFRP or damaged tire and the surfactant and hydrogen peroxide that are in contact with it
It heats together.Preferably, heating temperature is the temperature of the combustion reference temperature (500 DEG C to 800 DEG C) more than fixed carbon.Here,
Fixed carbon refer in carbonaceous refuse in the form of nonvolatile existing for carbide, including carbon fiber contained in discarded CFRP
Deng.
(2) ozone
As described above, as discarded CFRP or the contact method of damaged tire and ozone, for that will be discarded in closed container
CFRP or damaged tire are exposed to the method in the environmental gas containing ozone, or by discarded CFRP or damaged tire be impregnated into containing
Method etc. in the solution of ozone.Hereinafter, to the method being exposed in the environmental gas containing ozone and being impregnated into respectively
Method in Ozone Water is illustrated.In addition, as set forth above, it is possible to making the discarded CFRP contacted with ozone as suitably desired
Or the partial size of damaged tire reduces, or can also reduce partial size after surfactant is added drop-wise to CFRP or damaged tire.
(being exposed to the method in the environmental gas containing ozone)
The temperature of environmental gas containing ozone be preferably 5 DEG C or more 50 DEG C hereinafter, more preferably 10 DEG C or more 50 DEG C with
Under, further preferably 20 DEG C or more 50 DEG C or less.It, may be in discarded CFRP or damaged tire when at a temperature below 5 DEG C
Surface forms ice sheet, and hinders the discarded contact of CFRP or damaged tire with ozone.In addition, being needed when its temperature is more than 50 DEG C
Special heating device.
Using the method discarded CFRP or damaged tire being exposed in closed container in the environmental gas containing ozone
When, the injection mechanism and output mechanism, gas containing ozone of discarded CFRP or damaged tire can be set in the closed container
Introducing mechanism and output mechanism and the introducing mechanism and output mechanism that air can be imported into closed container when needed.
In addition, can be shared by two kinds of gases for the gas containing ozone and the introducing mechanism for air and output mechanism.
Further, it is preferable to ground, rabbling mechanism is provided in the closed container.By stirring discarded CFRP or useless wheel
Tire, facilitate partial size reduce after discarded CFRP or damaged tire all surface and ozone uniformly in contact with.Rabbling mechanism can be with
It is the equipment that stirring blade etc. is used for general powder particle agitating device, is also possible to wind-force mixing arrangement.
The ozone concentration in environmental gas contacted in closed container with discarded CFRP or damaged tire is preferably 100ppm
More than, more preferably 300ppm or more, particularly preferably 700ppm or more.When the ozone concentration in environmental gas is lower than 100ppm
When, it is elongated that discarded CFRP or damaged tire are exposed to the time in environmental gas, therefore, treatment effeciency reduces.It is discarded from improving
From the viewpoint of the flammability of CFRP or damaged tire, for the upper limit of the ozone concentration in environmental gas, there is no limit but when super
It when crossing 6000ppm, needs to be used to prepare the large scale equipment of ozone, therefore is not preferred.
In closed container, the exposure duration of CFRP or damaged tire in the environmental gas containing ozone is discarded depending on ring
Ozone concentration in the gas of border, but preferably 1 hour or more, more preferably 2 hours or more, particularly preferably 3 hours or more.When
When exposure duration was less than 1 hour, it may be unable to fully obtain ozone to the combustible improvement of discarded CFRP or damaged tire.
(being impregnated into the method in Ozone Water)
Then, it is illustrated to discarded CFRP or damaged tire are impregnated into the method in Ozone Water.
The temperature of Ozone Water be preferably 5 DEG C or more 30 DEG C hereinafter, more preferably 5 DEG C or more 25 DEG C hereinafter, particularly preferably 5
DEG C or more 20 DEG C or less.When the temperature of Ozone Water is lower than 5 DEG C, it is possible to create by freezing caused equipment fault, when more than 30
DEG C when, the ozone concentration decline in Ozone Water.
Preferably, the discarded dipping of CFRP or damaged tire in Ozone Water is carried out in closed container.Due to being closed
It carries out in container, therefore even if when the method for generating ozone gas by gas bubble method etc. prepares Ozone Water, it will not
Make ozone leakage that can recycle whole ozone to external container.In addition, in the case where the generation of ozone gas is less, it can also
To use open container.
Discarded CFRP or damaged tire and the volume ratio (Ozone Water/discarded CFRP or damaged tire) of the Ozone Water impregnated are excellent
It is selected as 1/1 or more, more preferably 2/1 or more, particularly preferably 4/1 or more.When discarded CFRP or damaged tire with impregnated
When the volume ratio of Ozone Water is less than 1/1, discarded CFRP or damaged tire may not be able to come into full contact with ozone.
Discarded CFRP or damaged tire are impregnated into the time in Ozone Water depending on the ozone concentration in Ozone Water, but preferably
It is 1 hour or more, more preferably 2 hours or more, particularly preferably 3 hours or more.When dip time was less than 1 hour, ozone
The combustible improvement of discarded CFRP or damaged tire may not be sufficient.
Preferably, rabbling mechanism is provided in the closed container.By stirring impregnated of discarded CFRP or damaged tire
Ozone Water, facilitate partial size reduce after discarded CFRP or damaged tire all surface and Ozone Water uniformly in contact with.Blender
Structure can be the equipment for general mud agitating device such as stirring blade.
In addition, being the wet of the discarded CFRP containing carbon fiber especially for hydrophobicity is improved when handling discarded CFRP
Lubricant nature, it is preferable that make to contain surfactant in Ozone Water.When the amount of Ozone Water is 100 mass parts, it is preferable that surface is living
Property agent usage amount be 0.01 mass parts or more 1 below the mass.When the usage amount of surfactant is less than 0.01 mass parts,
The wettability of the discarded CFRP of the carbon fiber containing high hydrophobicity may be unable to improve.Furthermore when being greater than 1 mass parts, Ke Nengwu
Method obtains the improvement of wettability corresponding with the usage amount of surfactant.
Finally, heating the discarded CFRP or damaged tire contacted with ozone in the inside of cement kiln.After being impregnated into Ozone Water,
It does not need that the discarded CFRP or damaged tire that are recycled is dried.In addition, being exposed in the environmental gas containing ozone
Or be impregnated into Ozone Water, air is placed into the discarded CFRP or damaged tire of combustible improvement result even if obtaining ozone
In, improved flammability will not reduce.
Discarded when carrying out the recuperation of heat or chemical recovery of the discarded CFRP or damaged tire in cement kiln, in cement kiln CFRP or
The investment position of damaged tire is not particularly limited, can on front side of the kiln (kiln burner side) or kiln tail side etc. it is any from put into,
In addition it is also possible to be used in calcining furnace.
But for discarding CFRP, it is preferable that put into the ignition temperature that temperature is more than the carbon fiber that discarded CFRP contains
The position of range (500 DEG C to 800 DEG C).
In addition, in the present embodiment, being illustrated with discarded CFRP or damaged tire for object to be processed, and to cement
Production equipment, that is, cement kiln is illustrated as the example of the burning facility of carbonaceous refuse, but in processing method of the invention
In, naturally it is also possible to it is burned using the burning facility in addition to cement kiln.
In addition, being illustrated to using a kind of example for discarding CFRP as object to be processed, but this is because the present invention
Method for carbide be carbon fiber the case where, extra high burning facilitation effect can be obtained.However, method of the invention
Object to be processed, be not limited to the waste for containing carbon fiber as carbide, for example, it can be damaged tires etc. to contain carbon
The waste of carbide other than fiber.
Embodiment
Then, the test result of processing method of the invention (that is, embodiment of processing method of the invention) is said
It is bright.
[test example 1]
It is tested, is come and keeping the size of carbonaceous refuse constant and changing the amount of surfactant and hydrogen peroxide
Evaluate the combustible influence of surfactant and hydrogen peroxide on carbonaceous refuse.Hereinafter, by the test, referred to as " flammability is commented
Valence test 1 ".
Specifically, each testing standard is set as shown below.
" test 1 "
Carbonaceous refuse: discarded CFRP (carbon fiber containing ratio: 58 mass %)
The sample size of discarded CFRP: average grain diameter 1mm
Hydrogen peroxide: and the special grade chemical (purity 30%) of Wako Pure Chemical Industries
Surfactant: the mixture of sodium n-alkylbenzenesulfonate, linear alkyl benzene sulfonic acid and alkyl ether sulphate sodium
(Lion Corporation's system: mother lemon (マ マ レ モ Application) (trade name))
The application method of surfactant and hydrogen peroxide: assuming that the environment vaporized in surfactant and hydrogen peroxide
The condition of lower exposed carbonaceous refuse, not by discarded CFRP it is pre-soaked into hydrogen peroxide in the case where, it is discarded to this
The hydrogen peroxide for being added to surfactant is added dropwise around CFRP, while being heated.Hydrogen peroxide and surfactant
Additive amount is as shown in table 1.
" test 2 "
Carbonaceous refuse: damaged tire
The sample size of damaged tire: 3 × 3 × 3mm
Hydrogen peroxide: identical as test 1
Surfactant: identical as test 1
The application method of surfactant and hydrogen peroxide: assuming that exposure is coated under the vaporized environment of hydrogen peroxide
The condition of the carbonaceous refuse of surfactant, by being added dropwise and being mixed into damaged tire by surfactant, not by surface
Be coated with surfactant the damaged tire it is pre-soaked into hydrogen peroxide in the case where, to it around hydrogen peroxide is added dropwise,
It is heated simultaneously.The coated weight of surfactant, the additive amount of hydrogen peroxide are as shown in table 2 in damaged tire.
In test 1 and test 2, above-mentioned sample is heated with 10 DEG C/min of heating rate, at 150 DEG C to 1000 DEG C
Within the temperature range of measure weight reduction rates.Using thermogravimetric amount differential heat determination device (Necci Japan Co. Ltd. system:
TG-DTA 2020SR (trade name)) measurement of weight reduction rates is carried out, and calculate weight reduction rates of weight at room temperature relatively
(non-volatile carbon: being largely carbon fiber when for CFRP to fixed carbon when the weight of (quality %) and the fixed carbon is 100%
Dimension) weight (in thermogravimetric curves, the weight of the starting point of the low gradient occurred at 500 DEG C to 600 DEG C with 800 DEG C or so
The difference of weight at the point of weight no longer reduction) in weight reduction rates (quality %).The former (weight relative to room temperature weight
Slip) it is equivalent to total combustion rate of discarded CFRP or damaged tire, the latter's (weight reduction rates of the weight relative to fixed carbon)
It is equivalent to the combustion rate of the fixed carbon in discarded CFRP or in damaged tire.
The test result of the flammability evaluation test 1 of discarded CFRP is as shown in table 1, and the results are shown in Table 2 for damaged tire.
[table 1]
[table 2]
As shown in table 1, it is being heated to 700 DEG C of stage, it is (real with the discarded CFRP of hydrogen peroxide and surfactant fluid
Example 1 is applied to embodiment 5) almost burn, in contrast, in the discarded CFRP not with hydrogen peroxide and surfactant fluid
(comparative example 1), only contacted with hydrogen peroxide and not and in the discarded CFRP (comparative example 2) of surfactant fluid, at this stage
About 30% combustion residue.Further, the flammability for comparing fixed carbon (carbon fiber) is using hydrogen peroxide and table
The embodiment 1 of face activating agent is being heated to 700 DEG C of stage into embodiment 5, and the fixed carbon (carbon fiber) discarded in CFRP is several
Completely burned, in contrast, do not use the comparative example 1 of hydrogen peroxide and surfactant, only use hydrogen peroxide and
It is not used in the comparative example 2 of surfactant, discards the combustion of the fixed carbon (carbon fiber) about 70% in CFRP at this stage
Burn residual.
In addition, as shown in table 2, being heated to 600 DEG C of stage, the damaged tire with hydrogen peroxide and surfactant fluid
(embodiment 6) almost burns, in contrast, the not damaged tire (comparative example 3) with hydrogen peroxide and surfactant fluid,
About 20% combustion residue at this stage.Further, the flammability for comparing fixed carbon (carbon fiber) is using peroxide
In the embodiment 6 for changing hydrogen and surfactant, it is being heated to 600 DEG C of stage, the fixed carbon (carbon fiber) in damaged tire is almost
Completely burned, in contrast, in not using the comparative example 3 of hydrogen peroxide and surfactant, at this stage in damaged tire
Fixed carbon about 60% combustion residue.
Fig. 1 shows the weight loss curves in the heating process of embodiment 3, comparative example 1 and comparative example 2.In addition, Fig. 2
Show the weight loss curves in embodiment 6 and the heating process of comparative example 3.Here, in the weight loss curves in figure
Occur in 3 regions that weight is reduced, two regions of low temperature side (corresponding to 300 to 400 DEG C of regions and correspond to 450 to
550 DEG C of region) the mainly reduction of the weight as caused by the burning of the fluid carbons such as resin, (550 DEG C of the weight loss zone of highest temperature side
Above region) the mainly reduction of the weight as caused by the burning of the fixed carbon such as carbon fiber.Therefore, by Fig. 1 and Fig. 2 it is found that originally
The method (embodiment 3, embodiment 6) of invention is especially effective to the flammability for promoting fixed carbon.Further, as shown in Figure 1, only
Addition hydrogen peroxide (comparative example 2) cannot obtain adequately burning facilitation effect.
[test example 2]
By changing the average grain diameter of carbonaceous refuse and making the amount of surfactant and hydrogen peroxide is constant to be tried
It tests, to evaluate the influence as caused by the average grain diameter of carbonaceous refuse.Hereinafter, the test is known as " partial size evaluation test 1 ".
Specifically, each testing standard is set as shown in following " test 3 ".
" test 3 "
Carbonaceous refuse: discarded CFRP (carbon fiber containing ratio: 58 mass %) identical with test example 1
The sample size of discarded CFRP: five kinds of average grain diameter 16mm, 9.5mm, 6.7mm, 4.75mm, 2.8mm
Hydrogen peroxide: identical as test example 1
Surfactant: identical as test example 1
The application method of surfactant and hydrogen peroxide: living about the hydrogen peroxide contacted with each discarded CFRP and surface
Property agent amount, when the amount of discarded CFRP is 100 mass parts, the amount of hydrogen peroxide (purity 30%) is 150 mass parts, and surface is living
Property agent amount be 5 mass parts (using the testing standard of the embodiment 3 of test example 1).
Above-mentioned discarded CFRP is put into as with hydrogen peroxide and surfactant before being put into following hot plates
It in product container, is heated 3 minutes in the electric furnace that temperature is set as 1400 DEG C of atmospheric environment, and evaluates the discarded CFRP after heating
In whether have unburned carbon fiber.The heating condition is the kiln front that cement kiln is put into simulation, then carries out burning processing
The case where condition.It is identical as above-mentioned flammability evaluation test 1 whether there is or not in the evaluation of unburned carbon contained fiber, after heating
Sample measurement thermogravimetric amount reduce, the weight in combustion reference temperature (500 to 800 DEG C) to find out fixed carbon (carbon fiber) subtracts
Few rate, in addition, the combustion reference temperature (500 to 800 DEG C) for equally finding out fixed carbon (carbon fiber) is interior for the sample before heating
Weight reduction rates, and using heat before to heat after combustion residue ratio as fixed carbon (carbon fiber) residual rate (matter
Amount %) it is evaluated.
The test result of partial size evaluation test 1 is as shown in table 3 below.
[table 3]
| The average grain diameter (mm) of discarded CFRP | The residual rate (quality %) of fixed carbon (carbon fiber) |
| 16 | 42 |
| 9.5 | 1.5 |
| 6.7 | 0 |
| 4.75 | 0 |
| 2.8 | 0 |
As shown in table 3, it is clear that when average grain diameter is 10mm hereinafter, when preferably 7mm or less, using surfactant and
The combination of hydrogen peroxide is bigger as the combustible improvement that processing promotor obtains.
[test example 3]
Keep the ozone concentration in the size and environment of discarded CFRP or damaged tire constant and changes in the ring containing the ozone
Exposure duration in border carrys out the flammability that CFRP or damaged tire are discarded in comparison.In addition, being impregnated into ozone for discarding CFRP
It is also compared under conditions of in water.Hereinafter, the test is known as " flammability evaluation test 2 ".
Specifically, each testing standard is set as shown below.
" test 4-1 "
Carbonaceous refuse: discarded CFRP (carbon fiber containing ratio: 58 mass %)
The sample size of discarded CFRP: average grain diameter 1mm
Ozone contact method: it is exposed to the environment (20 DEG C) containing ozone
Environment: ozone concentration 500ppm
Exposure condition: by the above-mentioned discarded CFRP of 1g put into 50ml closed container (with environmental gas introducing mechanism,
Output mechanism), and continue to flow into above-mentioned environment with 4L/ minutes speed.
Exposure duration: 0 hour (comparative example 4), 1 hour (embodiment 7), 3 hours (embodiment 8)
" test 4-2 "
Carbonaceous refuse: discarded CFRP (carbon fiber containing ratio: 58 mass %)
The sample size of discarded CFRP: average grain diameter 1mm
Ozone contact method: it is impregnated into the Ozone Water added with surfactant
Ozone Water: ozone concentration 50ppm
Surfactant: the mixture of sodium n-alkylbenzenesulfonate, linear alkyl benzene sulfonic acid and alkyl ether sulphate sodium
(Lion Corporation's system: mother lemon (マ マ レ モ Application) (trade name))
Surfactant concentration: it is the Ozone Water of 100 mass parts relative to total amount, is 0.01 mass parts (0.01 matter
Measure %)
Immersion condition: the above-mentioned discarded CFRP of 1g is put into 100ml and is contained in the Ozone Water of surfactant, and is closed the lid
Son is stood.
Exposure duration: 1 hour (embodiment 9)
" test 5 "
Carbonaceous refuse: damaged tire
The sample size of damaged tire: 3 × 3 × 3mm
Ozone contact method: it is exposed to the environment (20 DEG C) containing ozone
Environment: ozone concentration 500ppm
Exposure condition: 1 above-mentioned damaged tire piece is put into closed container (the importing machine with environmental gas of 50ml
Structure, output mechanism), and continue to flow into above-mentioned environment with 4L/ minutes speed.
Exposure duration: 0 hour (comparative example 5), 1 hour (embodiment 10), 3 hours (embodiment 11)
The sample after exposure obtained or dipping is heated with 10 DEG C/min of heating rate, and in room temperature to 1000 DEG C
Within the temperature range of measure weight reduction rates.Using thermogravimetric amount differential heat determination device (Necci Japan Co. Ltd. system:
TG-DTA 2020SR (trade name)) measurements of weight reduction rates is carried out, it is identical as test example 1, calculate discarded CFRP or damaged tire
Total combustion rate and discarded CFRP in or fixed carbon in damaged tire combustion rate.
The test result of the flammability evaluation test 2 of discarded CFRP is as shown in table 4 and table 5, the result of damaged tire such as 6 He of table
Shown in table 7.In addition, respective thermogravimetric curves are as shown in Figure 3 and Figure 4.
[table 4]
[table 5]
[table 6]
[table 7]
As shown in figure 4, the discarded CFRP (embodiment 7 to embodiment 9) for being exposed to ozone environment or being impregnated into Ozone Water
It is being heated to 750 DEG C of stage completely burned, in contrast, in the comparative example 4 not contacted with ozone, about 10% combustion
Burn residual.Further, as shown in table 5, the flammability for comparing fixed carbon (carbon fiber), in the embodiment 7 contacted with ozone
Into embodiment 9, it is being heated to 750 DEG C of stage, is discarding fixed carbon (carbon fiber) completely burned in CFRP, in contrast,
In the comparative example 4 not contacted with ozone, the fixed carbon imperfect combustion if not being heated to 800 DEG C.
In addition, when comparing the discarded CFRP (embodiment 7 and embodiment 8) being exposed in ozone environment and being impregnated into containing table
When discarded CFRP (embodiment 9) in the Ozone Water of face activating agent, combustion rate when for 700 DEG C before carbon completely burned,
In total combustion rate (table 4) and the combustion rate (table 5) of fixed carbon (carbon fiber), exposure 3 hours in the ozone environment of 500ppm
Impregnated of the embodiment of short period i.e. 1 hour in embodiment 8 and the Ozone Water of the ozone concentration in the 50ppm lower than its concentration
9 is roughly the same.Therefore, the contact method as carbonaceous refuse and ozone, it is believed that preferred method is by carbonaceous waste
Gurry is impregnated into the method in Ozone Water.
Then, as shown in table 6, the damaged tire (embodiment 10 and embodiment 11) being exposed in ozone environment is being heated to
600 DEG C of stage completely burned, in contrast, in the comparative example 5 not contacted with ozone, it is endless if not being heated to 650 DEG C
Full burning.Further, as shown in table 7, the flammability for comparing fixed carbon, in the embodiment 10 and embodiment contacted with ozone
In 11, be heated to 580 DEG C of stage, the fixed carbon completely burned in damaged tire, in contrast, not and ozone contact ratio
Compared in example 5, there is 10% combustion residue if not being heated to 600 DEG C.
Further, since the combustion rate of embodiment 10 and embodiment 11 is roughly the same, it can be considered that the exposure of damaged tire
Even if the time less than 1 hour, can also obtain sufficient combustible improvement.
[test example 4]
For discard CFRP, carried out change average grain diameter when combustion rate evaluation.Hereinafter, the test is known as " grain
Diameter evaluation test 2 ".
Use discarded CFRP identical with flammability evaluation test 2 as the sample of partial size evaluation test 2, and makes average
Partial size is five kinds of samples of 16mm, 9.5mm, 6.7mm, 4.75mm, 2.8mm.
The ozone environment use contacted with each sample environment identical with flammability evaluation test 2, and discarded CFRP is made to exist
The time of exposure is 3 hours (identical as the embodiment 8 of flammability evaluation test 2) in ozone environment.As comparative example, prepare
The sample (identical as the comparative example 4 of flammability evaluation test 2) of exposure not in ozone environment.
Above-mentioned sample is heated 3 minutes in the electric furnace that temperature is set as 1400 DEG C of atmospheric environment, and with 2 phase of test example
With ground, the residual rate of unburned and remaining fixed carbon (carbon fiber) in the sample after evaluation heating.
The test result of partial size evaluation test 2 is as shown in table 8.
[table 8]
As shown in table 8, it is clear that when average grain diameter is 10mm hereinafter, when preferably 7mm or less, use ozone as handling
The combustible improvement that promotor obtains is bigger.
Claims (12)
1. a kind of processing method of carbonaceous refuse, it is characterised in that: for the processing of the carbonaceous refuse of burning carbonaceous refuse
Method,
After contacting the carbonaceous refuse with the processing promotor containing following (1) or following (2), it is carbon containing discarded to burn this
Object,
(1) surfactant and hydrogen peroxide,
(2) ozone.
2. the processing method of carbonaceous refuse according to claim 1, it is characterised in that:
The processing promotor includes (1) surfactant and hydrogen peroxide, makes the carbonaceous refuse and surface-active
Agent contacts and reduces partial size, after further contacting it with hydrogen peroxide, burns the carbonaceous refuse.
3. the processing method of carbonaceous refuse according to claim 1 or 2, it is characterised in that:
The processing promotor includes (1) surfactant and hydrogen peroxide, when the amount of the carbonaceous refuse is 100 matter
When measuring part, the amount of the hydrogen peroxide be 15 mass parts or more and 100 below the mass.
4. the processing method of carbonaceous refuse described in any one of claim 1 to 3, it is characterised in that:
The processing promotor includes (1) surfactant and hydrogen peroxide, when the amount of the hydrogen peroxide is 100 mass
Part when, the amount of the surfactant be 0.01 mass parts or more and 25 below the mass.
5. the processing method of carbonaceous refuse according to claim 1, it is characterised in that:
The processing promotor includes described (2) ozone, make the ozone with ozone concentration 100ppm or more and 6000ppm with
Under gas form contacted with the carbonaceous refuse.
6. the processing method of carbonaceous refuse according to claim 1, it is characterised in that:
The processing promotor includes described (2) ozone, make the ozone with ozone concentration 1ppm or more and 50ppm it is below
Liquid form is contacted with the carbonaceous refuse.
7. the according to claim 1, processing method of carbonaceous refuse described in 5 or 6, it is characterised in that:
The processing promotor includes that described (2) ozone further makes the carbonaceous refuse and surfactant fluid.
8. the processing method of carbonaceous refuse according to claim 7, it is characterised in that:
The processing promotor includes described (2) ozone, makes the carbonaceous refuse and surfactant fluid and reduces partial size,
After further contacting it with ozone, the carbonaceous refuse is burned.
9. the processing method of carbonaceous refuse according to any one of claims 1 to 7, it is characterised in that:
The average grain diameter of the carbonaceous refuse is 10mm or less.
10. the processing method of carbonaceous refuse described according to claim 1~any one of 8, it is characterised in that:
The carbonaceous refuse is selected from by discarding CFRP, BOF, ASR, RPF, RDF, sawdust, damaged tire, rubber scrap, water suction
Property the waste of polymer, municipal refuse, the waste of thermosetting property and/or thermoplastic resin, discarded FRP, carbon fiber waste,
The waste of one or more of the group of the waste of optical fiber waste and solar battery composition.
11. the processing method of carbonaceous refuse described according to claim 1~any one of 9, it is characterised in that:
The carbonaceous refuse includes carbon fiber.
12. the processing method of carbonaceous refuse described according to claim 1~any one of 10, it is characterised in that:
After contacting the carbonaceous refuse with the processing promotor, the carbonaceous refuse is burned in cement manufacture plant.
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| JP2016191688 | 2016-09-29 | ||
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| JP2017-029529 | 2017-02-20 | ||
| JP2017029529A JP6858589B2 (en) | 2016-09-29 | 2017-02-20 | Carbon-containing waste treatment method |
| JP2017-029722 | 2017-02-21 | ||
| JP2017029722A JP6762890B2 (en) | 2017-02-21 | 2017-02-21 | Carbon-containing waste treatment method |
| PCT/JP2017/025384 WO2018061404A1 (en) | 2016-09-29 | 2017-07-12 | Method for treating carbon-containing waste |
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| JP2001261883A (en) * | 2000-03-23 | 2001-09-26 | Okayama Prefecture | Method of reclaiming vulcanized rubber |
| JP2007131463A (en) * | 2005-11-08 | 2007-05-31 | Ube Ind Ltd | Method of treating waste plastic containing carbon fiber |
| JP2011023793A (en) * | 2009-07-13 | 2011-02-03 | Oki Electric Industry Co Ltd | Subscriber terminal, optical communication network, and method of adjusting intensity of light signal in the optical communication network |
| CN202675299U (en) * | 2012-05-29 | 2013-01-16 | 天津辰创环境工程科技有限责任公司 | Device for combusting nitrogen-containing organic wastes |
| JP2015160888A (en) * | 2014-02-27 | 2015-09-07 | 株式会社東芝 | Treatment method and treatment equipment of used ion exchange resin |
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