CN104371178A - Method for preparing high polymer composite material by taking garbage power generation flying ash as raw material - Google Patents
Method for preparing high polymer composite material by taking garbage power generation flying ash as raw material Download PDFInfo
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- CN104371178A CN104371178A CN201410679219.9A CN201410679219A CN104371178A CN 104371178 A CN104371178 A CN 104371178A CN 201410679219 A CN201410679219 A CN 201410679219A CN 104371178 A CN104371178 A CN 104371178A
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- flying dust
- flying ash
- power generation
- composite material
- polymer composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
The invention discloses a method for preparing a high polymer composite material by taking garbage power generation flying ash as a raw material, belongs to the technical field of subsequent treatment of waste incineration power generation and in particular relates to a treatment process of flying ash generated during waste incineration power generation. The method comprises the following steps: performing heat treatment on waste incineration power generation flying ash, grinding the flying ash into powder, and blending and shearing the powdered flying ash and a thermoplastic polymer material to prepare a flying ash and high polymer composite material. According to the method disclosed by the invention, the waste incineration flying ash is ingeniously utilized, the cost consumption of passive flying ash treatment is avoided due to the method, a novel path of the product is obtained, the flying ash serves as an inorganic filler in the high polymer composite material, and a complete flying ash treatment and reproduction process chain is formed.
Description
Technical field
The invention belongs to the subsequent disposal technical field of waste incineration and generating electricity, the treatment process of the flying dust of particularly waste incineration and generating electricity production.
Background technology
Widely use with the generation technology of burning away the refuse at present, the pair of producing owing to burning away the refuse is biological---and flying dust has then become burden, owing to containing the higher arsenic that can be flooded out, strontium, bismuth in flying dust, the multiple harmful heavy metal material such as rubidium and salt, and the Dioxins highly toxic substance produced in Refuse Incineration Process also can be enriched in flying dust.
According to the standard of the existing process Hazardous wastes of China, the legal process outlet of flying dust produced for waste incineration and generating electricity is filled up into security landfill field.And this standard and the direct contradiction of enforcement are, major part in the city in garbage burning factory or power station is had in China does not have security landfill field, needs to take the techniques such as pressure brick-landfill, and this will certainly bring certain processing cost.The mode of process flying dust has several, wherein it can not be made to stablize at landfill yard only by adding cement or alkaline matter, because flying dust relative to amount environment very little, is not enough to have an impact to the pH value of overall situation.Therefore, adopt current filling type process flying dust not only can not give full play to its economic worth, and a series of technique can be produced expend.
In addition, make by the mode of solidification, melting a kind of method that building materials are also effective utilizations, but this process is oversize, also there is no a kind of solution preferably at present, also need to do much to probe into.
Summary of the invention
The flying dust that the present invention produces after being intended to realize waste incineration and generating electricity carries out harmless treatment, with reach play flying dust economic worth, reduce objectionable impurities-Dioxins on the object of the impact of environment.
Technical solution of the present invention is: be first ground into powder after Overheating Treatment by the flying dust of waste incineration and generating electricity, then by after pulverous flying dust and the blended shearing of thermoplastic macromolecule material, makes flying dust and high molecular matrix material.
Owing to containing higher multiple harmful heavy metal material, salt and the Dioxins such as the arsenic that can be flooded out, strontium, bismuth, rubidium in flying dust, so the heat treating method that this invention takes high temperature sintering is to reducing the heavy metal content in flying dust, and the solubility rate of heavy metal in flying dust is reduced; Select thermoplastic macromolecule material as body material, to reach the sealing process to metallics.
The present invention adopts starting raw material flying dust to be by product after garbage power, flying dust after thermal treatment is added in macromolecular material with the form of mineral filler by the present invention, utilize polymer heavy metal ion to carry out sealing process on the one hand, realize heavy metal ion and ooze out without immersion; On the other hand, the effect reaching and reduce polymer manufacturing cost and strengthen high molecular chemical characters is filled in macromolecule matrix with flying dust.
The present invention have selected polymer interpenetrating network system as research object, particularly organic/inorganic polymer composite system, this system overcomes the defect of single-material and conventional composite materials performance, combine the advantage (as high thermal stability, rigidity) of inorganic materials and the advantage (as dielectricity, ductility and elasticity) of macromolecular material, not only achieve flying dust carcinogenic toxicity material---the closed antiseepage of Dioxins and heavy metal, and extra performance raising is produced by forming inierpeneirating network structure between two components.
To sum up, the present invention is under little cost conditions, make use of incineration of refuse flyash dexterously, the method had both been conducive to the cost consumption avoiding the passive process of flying dust, obtain the approach of new goods simultaneously, using flying dust as the mineral filler in polymer composite, define complete flying dust process and regenerative ratio technology chain.
In order to improve the consistency between fly ash granule and macromolecule matrix, the present invention, when blended shearing, also can add surface-modifying agent.
Described heat treated temperature of the present invention is 500 ~ 1000 DEG C.Show according to thermal gravimetric analysis results, along with the rising of temperature, the quality of flying dust presents stair-stepping decline.Comparatively obvious after 500 DEG C, analyze and learn that the crystalline phase composition of the thermal treatment of middle high temperature to flying dust has positive change, serve advantageous effect to the decomposition of organism (containing hazardous and noxious substances), more follow-up Compound Machining provides excellent raw material.
For fineness≤100 order of the pulverous flying dust with the blended shearing of thermoplastic macromolecule material.Flying dust is granule type packing material in macromolecular material compound system, and flying dust is inorganic crystalline phase system.The specific surface area of particle is little, and has good interface cohesion with polymkeric substance.The fineness of flying dust is less, also has the effects such as reinforcement to a certain extent to whole composite system
Temperature of charge during blended shearing is 200 ± 10 DEG C.At about 200 DEG C, the macromolecule matrix such as polypropylene or polyethylene material can be good at melting, has good processing characteristics, and is no more than degradation temperature to base material not damaged.
The time of blended shearing is 10min.The setting of this time based on test turnout and determine, the 10min time can ensure inorganic phase and the good melt blending of organic polymer material, and is also conducive to the facilitation effect of the auxiliary agents such as coupling agent.Time is too short, and two-phase system can not be well compatible, and overlong time, lowers efficiency first, second can be polymer base material degradation.Adjustment process period and processing temperature to be taken the circumstances into consideration according to yield in unit time in actual production process.
Described thermoplastic macromolecule material is: polyethylene, polypropylene or polyvinyl chloride.
The preferred thermoplastic macromolecule material of the present invention is polypropylene in addition, to reach the sealing process to metallics.
Accompanying drawing explanation
The flying dust that Fig. 1 is fly ash content when being 10phr and the profile scanning electromicroscopic photograph of polypropylene composite material.
The flying dust that Fig. 2 is fly ash content when being 20phr and the profile scanning electromicroscopic photograph of polypropylene composite material.
The flying dust that Fig. 3 is fly ash content when being 30phr and the profile scanning electromicroscopic photograph of polypropylene composite material.
Fig. 4 is the profile scanning electromicroscopic photograph of flying dust/polypropylene composite material after the KH-550 surface modification with 0.5wt%.
Fig. 5 is the profile scanning electromicroscopic photograph of flying dust/polypropylene composite material after the KH-550 surface modification with 1wt%.
Fig. 6 is the profile scanning electromicroscopic photograph of flying dust/polypropylene composite material after the KH-550 surface modification with 1.5wt%.
Embodiment
Embodiment 1
1, the waste incineration and generating electricity of certain mass is produced flying dust to heat-treat in retort furnace, thermal creep stress 500 ~ 1000 DEG C, according to the different flying dust amount control treatment time.Carry out milled processed after being cooled to room temperature, and through 100 object sieves, get the fly ash powder sieved.
2, according to certain ratio, fly ash powder and granular polypropylene are carried out melt blending in the blended instrument of electrically heated, the processing temperature of selection is 200 DEG C, and time controling is at 10min.Under the effect of high temperature and shearing force, fly ash powder is dispersed in polypropylene matrix, and two-phase system presents good distribution.Finally flying dust and the preparation of polyacrylic matrix material are become test specimens product and carry out Mechanics Performance Testing.
The flying dust of this test gets 0:100,10:90,20:80 and 30:70 with polyacrylic mixing quality than respectively, can observe the flying dust/polypropylene composite material mechanical performance data of table 1 to the test of flying dust and polypropylene composite material mechanical property.
As known from Table 1: along with the add-on of flying dust improves, the Young's modulus of polypropylene material increases, the hardness of material increases, and its tensile strength declines to some extent due to the increase of fly ash content, but the range of decrease is less, about 19%, when fly ash content reaches 30phr, its tensile strength still can remain on 28.99MPa.The improvement of matrix material tensile strength has benefited from inserting of nano level fly ash powder, and when flying dust add-on is 20phr, the shock strength of resulting materials promotes 33%.
The present invention, by composite technology means, not only have found the outlet of flying dust process, the use properties of polypropylene material of equally also having refreshed oneself to a certain extent.
Table 1 is flying dust/polypropylene composite material mechanical property
From Fig. 1,2 and 3 different fly ash contents, the profile scanning electromicroscopic photograph of flying dust and polypropylene composite material is visible: material presents typical brittle rupture feature.Fly ash granule in polypropylene matrix presents well distributed.Matrix section also exists the defects such as certain cavity, and this may due to the not good caused desorption phenomenon of particle in drawing process of the interface compatibility between fly ash granule and polypropylene matrix.
Embodiment 2
1, the flying dust of certain mass is heat-treated in retort furnace, thermal creep stress 500 ~ 1000 DEG C, according to the different flying dust amount control treatment time.Carry out milled processed after being cooled to room temperature, and through 100 object sieves, get the fly ash powder sieved.
2, according to certain ratio, fly ash powder and granular polypropylene are carried out melt blending in Haake torque rheometer, and add appropriate surface-modifying agent (KH-550/KH-560).The processing temperature adopted is 200 DEG C, and time controling is at 10min.Under the effect of high temperature and shearing force, fly ash powder is dispersed in polypropylene matrix, and two-phase system presents good distribution.Finally polypropylene/fly-ash compsite material preparation is become test specimens product and carries out Mechanics Performance Testing.
This example adds surface-modifying agent and is intended to improve the consistency between fly ash granule and macromolecule matrix, different surfaces properties-correcting agent can be adopted to process for fly ash granule surface according to different objects.Table 2 gives the mechanical property adopting polypropylene composite material after common surface modification.
As seen from Table 2: by the raising changed into along with surface modification dosage of the composite materials property after process, the tensile strength of flying dust and polypropylene composite material obtains obvious lifting, and when coupling agent content is 0.5 wt%, tensile strength reaches the highest; Meanwhile, in shock strength, along with the lifting of coupling agent content, the shock strength of material continues to promote.From this angle, adding of surface-modifying agent has lifting to a certain degree to the interface compatibility of inorganic-organic composite material, and under ensureing that polypropylene material has the prerequisite of better use properties, the content of flying dust can also further promote.
Table 2 is flying dust after surface modification/polypropylene composite material mechanical property
From Fig. 4,5 and 6: fly ash granule is well embedded in polypropylene matrix, the consistency of fly ash granule and matrix obtains improvement to a certain degree, especially appear in the base the phenomenon running through fracture in drawing process from granule interior, the interface bond strength of side light between obturator and matrix improves.
Embodiment 3
1, the flying dust of certain mass is heat-treated in retort furnace, thermal creep stress 500 ~ 1000 DEG C, according to the different flying dust amount control treatment time.Carry out milled processed after being cooled to room temperature, and through 100 object sieves, get the fly ash powder sieved.
2, according to certain ratio, fly ash powder and granular polyethylene are carried out melt blending in the blended instrument of electrically heated, the processing temperature of selection is 210 DEG C, and time controling is at 10min.Under the effect of high temperature and shearing force, fly ash powder is dispersed in base polyethylene, and two-phase system presents good distribution.Finally flying dust and the preparation of poly matrix material are become test specimens product and carry out Mechanics Performance Testing.
The flying dust of this test gets 0:100,20:80,30:70 and 40:60 with poly mixing quality than respectively, can observe the flying dust/composite polyethylene material mechanical performance data of table 3 to the test of flying dust and composite polyethylene material mechanical property.
As known from Table 3: along with the raising of flying dust add-on, each mechanical property of matrix material has obvious change.Modulus in flexure and flexural strength all improve; Shock strength presents first increases rear downward trend; The enhancing of tensile modulus adds remarkable lifting due to rigid particles, but tensile strength then declines to some extent, and the range of decrease is about 21%.The part of material property reduces can by adding auxiliary agent to improve, and overall performance presents good lifting trend.
Table 3 is flying dust/composite polyethylene material mechanical property
Embodiment 4
1, the flying dust of certain mass is heat-treated in retort furnace, thermal creep stress 500 ~ 1000 DEG C, according to the different flying dust amount control treatment time.Carry out milled processed after being cooled to room temperature, and through 100 object sieves, get the fly ash powder sieved.
2, according to certain ratio, fly ash powder and granular polyvinyl chloride are carried out melt blending in the blended instrument of electrically heated, the processing temperature of selection is 190 DEG C, and time controling is at 10min.Under the effect of high temperature and shearing force, fly ash powder is dispersed in PVC base system, and two-phase system presents good distribution.Finally the preparation of the matrix material of flying dust and polyvinyl chloride is become test specimens product and carry out Mechanics Performance Testing.
The flying dust of this test gets 0:100,5:95,10:90 and 15:85 with the mixing quality of polyvinyl chloride than respectively, can observe the flying dust/polyvinyl chloride composite materials mechanical performance data of table 4 to the test of flying dust and polyvinyl chloride composite materials mechanical property.
As known from Table 4: along with the raising of flying dust add-on, each mechanical property of matrix material has obvious change.Tensile strength has a declining tendency, and more obvious along with the lifting of flying dust add-on; Flexural strength presents the trend first increasing and reduce afterwards, reaches maximum when the add-on of flying dust is 5phr; Flying dust is inorganic rigid particle, and shock strength also increases due to the hardness increase of material, but not too obvious
Table 4 is flying dust/polyvinyl chloride composite materials mechanical property
Change polyvinyl chloride in this example into polystyrene, go out the product that can obtain roughly the same performance equally.
Claims (7)
1. with garbage power flying dust for the method for polymer composite prepared by raw material, it is characterized in that first the flying dust of waste incineration and generating electricity being ground into powder after Overheating Treatment, again by after pulverous flying dust and the blended shearing of thermoplastic macromolecule material, make flying dust and high molecular matrix material.
2. method according to claim 1, adds surface-modifying agent when it is characterized in that blended shearing.
3. method according to claim 1 or 2, is characterized in that described heat treated temperature is 500 ~ 1000 DEG C.
4. method according to claim 1 or 2, is characterized in that fineness≤100 order for the pulverous flying dust with the blended shearing of thermoplastic macromolecule material.
5. method according to claim 1 or 2, temperature of charge when it is characterized in that blended shearing is 200 ± 10 DEG C.
6. method according to claim 5, is characterized in that the time of blended shearing is 10min.
7. method according to claim 1, is characterized in that described thermoplastic macromolecule material is: polyethylene, polypropylene, polystyrene or polyvinyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410679219.9A CN104371178A (en) | 2014-11-24 | 2014-11-24 | Method for preparing high polymer composite material by taking garbage power generation flying ash as raw material |
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| CN201410679219.9A CN104371178A (en) | 2014-11-24 | 2014-11-24 | Method for preparing high polymer composite material by taking garbage power generation flying ash as raw material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107245167A (en) * | 2017-07-13 | 2017-10-13 | 浙江工业大学温州科学技术研究院 | A kind of compounded rubber reinforcing agent and its preparation method and application |
| CN107337834A (en) * | 2017-07-13 | 2017-11-10 | 浙江工业大学温州科学技术研究院 | A kind of incineration of refuse flyash filling master batch and its preparation method and application |
| CN110204233A (en) * | 2019-04-28 | 2019-09-06 | 武汉理工大学 | A kind of preparation method and heat preserving and insulating material of Polystyrene flyash |
| CN113351621A (en) * | 2021-06-01 | 2021-09-07 | 成都锐思环保技术股份有限公司 | Method for recycling high-salt-content product with zero emission of desulfurization wastewater |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245167A (en) * | 2017-07-13 | 2017-10-13 | 浙江工业大学温州科学技术研究院 | A kind of compounded rubber reinforcing agent and its preparation method and application |
| CN107337834A (en) * | 2017-07-13 | 2017-11-10 | 浙江工业大学温州科学技术研究院 | A kind of incineration of refuse flyash filling master batch and its preparation method and application |
| CN107245167B (en) * | 2017-07-13 | 2019-10-29 | 浙江工业大学温州科学技术研究院 | A kind of compounded rubber reinforcing agent and its preparation method and application |
| CN107337834B (en) * | 2017-07-13 | 2020-04-21 | 浙江工业大学温州科学技术研究院 | Waste incineration fly ash filling master batch and preparation method and application thereof |
| CN110204233A (en) * | 2019-04-28 | 2019-09-06 | 武汉理工大学 | A kind of preparation method and heat preserving and insulating material of Polystyrene flyash |
| CN113351621A (en) * | 2021-06-01 | 2021-09-07 | 成都锐思环保技术股份有限公司 | Method for recycling high-salt-content product with zero emission of desulfurization wastewater |
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Application publication date: 20150225 |