CN104192822B - A kind of method of polyvinylidene chloride scrap concrete recycling - Google Patents
A kind of method of polyvinylidene chloride scrap concrete recycling Download PDFInfo
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- CN104192822B CN104192822B CN201410354557.5A CN201410354557A CN104192822B CN 104192822 B CN104192822 B CN 104192822B CN 201410354557 A CN201410354557 A CN 201410354557A CN 104192822 B CN104192822 B CN 104192822B
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Abstract
The method that the invention discloses a kind of polyvinylidene chloride scrap concrete recycling, (a) will pulverize after polyvinylidene chloride garbage, alkali metal hydroxide and plasticizer are by being stirred mixing, extruding pelletization at a temperature of 170～200 DEG C after constant weight number proportioning；B granulation material in atmosphere of inert gases, is warming up to 700～800 DEG C by 25 DEG C with two kinds of different heating rates, then is down to 25 DEG C with the speed of 10～20 DEG C/min, obtain carbonated material by () in two steps；C carbonated material is immersed in phenolic resin alcoholic solution 1～2h by (), in atmosphere of inert gases, be warming up to 850～900 DEG C by 25 DEG C in two steps with two kinds of different heating rates, then be down to 25 DEG C with the speed of 5～10 DEG C/min, obtain porous carbon materials.Present invention process is simple, environmental protection, low cost, good in economic efficiency.
Description
Technical field
The method that the present invention relates to scrap concrete recycling, specific to relating to a kind of polyvinylidene chloride scrap concrete
The method of recycling.
Background technology
Polyvinylidene chloride is currently widely used for the fields such as packaging for foodstuff, chinampa, wig, netting twine.Poly-inclined
The Litter etc. after substantial amounts of waste material, leftover pieces and use is inevitably produced during the processing of dichloroethylene and use
Garbage.Owing to polyvinylidene chloride the most easily decomposes, polyvinylidene chloride scrap concrete reworking is caused to be stranded
Difficult；Use directly to burn and cause environmental pollution, and power consumption height.
Porous carbon materials is the novel nonpolar carbonaceous sorbent material of the one grown up the sixties in 20th century.Porous carbon
Material even aperture distribution, has the highest chemical stability and gas-selectively, and current porous carbon materials has been widely used
Each in environmental conservation, chemical industry, petroleum industry, food processing, hydrometallurgy, refined, the militarization protection of medicine etc.
Individual field.
The raw material preparing porous carbon materials is extensive, mainly includes machine high molecular polymer (Saran resin (poly-inclined dichloro
Ethylene), phenolic resin etc.), various coal and coal radical derivative (brown coal, bituminous coal, anthracite etc.), biomass (timber,
Shell, bagasse etc.), petroleum by-products (petroleum residue, petroleum coke, asphalt etc.), the difference of raw material make system
Standby porous carbon materials technique is different, and the performance of the porous carbon materials obtained is the most different.Porous carbon is prepared it addition, existing
The method of material is relatively costly.Therefore find a kind of cheaper starting materials to be easy to get, the porous carbon that the properties of product that prepare are stable
The preparation method of material, is to need the urgent problem solved.
Under certain condition, dechlorination, formation double bond, generation Diels-Alder reacts cyclization, can obtain polyvinylidene chloride
Porous carbon materials product.Therefore, utilize polyvinylidene chloride garbage to prepare porous carbon materials, can effectively process poly-
Vinylidene chloride garbage, can turn waste into wealth again, it is thus achieved that the porous carbon materials of high added value.But polyvinylidene chloride is discarded
Containing the multiple processing aid added in polyvinylidene chloride processing preparation process in thing, such as plasticizer, lubricant, resist
Oxygen agent etc., additionally polyvinylidene chloride is different according to synthesis technique, and the polyvinylidene chloride product composition obtained is complicated, bag
Include the homopolymer of vinylidene chloride or vinylidene chloride and acrylate or the copolymer of chloroethylene copolymer, hence with poly-partially
The porous carbon materials that properties of product that dichloroethylene garbage prepares are stable, difficulty is very big, need to overcome composition of raw materials,
Many technical barriers such as preparation process and parameter.At present, utilize polyvinylidene chloride garbage to prepare porous carbon materials also
Rarely has report.
Summary of the invention
The technical problem to be solved in the present invention is the defect overcoming prior art, it is provided that a kind of technique is simple, environmental protection,
Low cost, the method for good in economic efficiency polyvinylidene chloride scrap concrete recycling.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions: a kind of polyvinylidene chloride gives up
The method of gurry recycling, comprises the following steps:
(a) by weight, will pulverize after polyvinylidene chloride garbage 85～95 parts, alkali metal hydroxide
3～8 parts, plasticizer 2～7 parts, under 200～400rpm rotating speeds after stirring mixing, through double spiral shells at a temperature of 170～200 DEG C
Bar extruder extruding pelletization, obtains granulation material；
B granulation material that step (a) is obtained by () is in atmosphere of inert gases, with heating rate 5～10 DEG C/min by 25 DEG C
It is warming up to 400～500 DEG C, constant temperature 1～2h, then it is warming up to 700～800 DEG C with heating rate 10～15 DEG C/min, constant temperature 2～3h
Carry out carbonization, be then down to 25 DEG C with the rate of temperature fall of 10～20 DEG C/min, obtain carbonated material；
C carbonated material that () step (b) obtains takes out, at noble gas atmosphere after immersing in phenolic resin alcoholic solution 1～2h
In enclosing, it is warming up to 500～600 DEG C with heating rate 10～15 DEG C/min by 25 DEG C, constant temperature 1～2h, then with heating rate
2.5～5 DEG C/min is warming up to 850～900 DEG C, constant temperature 2～3h, is then down to 25 DEG C with the rate of temperature fall of 5～10 DEG C/min,
Obtain porous carbon materials.
As the preferred embodiment of the present invention, the alkali metal hydroxide described in step (a) is KOH, NaOH,
Ca(OH)2、Mg(OH)2In the mixture of one or more.
As the preferred embodiment of the present invention, the plasticizer described in step (a) is methyl methacrylate/acrylic acid ester
One or both mixture in copolymer, epoxy soybean oil.
As the preferred embodiment of the present invention, during extruding pelletization described in step (a), material is in double screw extruder
The time of staying be 15-25 minute.
As the preferred embodiment of the present invention, the phenolic resin alcoholic solution described in step (c) is that phenolic resin methanol is molten
The mixture of one or more in liquid, phenolic resin ethanol solution, phenolic resin butanol solution.
As the preferred embodiment of the present invention, described phenolic resin alcoholic solution concentration is 5～20wt.%.
As the preferred embodiment of the present invention, described porous carbon blanking aperture is 50-500nm, and specific surface area is
600-1500m2/g。
Polyvinylidene chloride garbage of the present invention is in the polyvinylidene chloride course of processing or uses produced limit
Litter etc. after corner material, waste material, use, as raw material for standby after smashing polyvinylidene chloride garbage.
The present invention makes a certain proportion of polyvinylidene chloride garbage, alkali metal hydroxide and increasing by step (a)
Mould agent mix homogeneously, simultaneously in melting process, polyvinylidene chloride garbage generation preliminary exposition, and then obtain step
Granulation material needed for (b).
The proportioning of raw material has considerable influence, reasonable preparation raw material to the mechanical property of porous carbon materials and preparation condition and step
Proportioning be the committed step obtaining high performance porous carbon materials.Polyvinylidene chloride has added multiple in preparation process
Processing aid, such as plasticizer, lubricant, antioxidant etc., polyvinylidene chloride garbage is during reprocessing, it is only necessary to
Add the most a small amount of plasticizer so that smooth extrusion molding in twin screw extrusion, for reducing porous carbon materials system
Standby cost, the plasticizer consumption used in the present invention is preferably 2-7 part.For ensureing the plasticizer added and gathering inclined dichloro
Ethylene garbage has the good compatibility, it is to avoid produces split-phase in raw mixture, and then affects the hole of porous carbon materials
Footpath uniformity, plasticizer is the mixed of one or both in methyl methacrylate/acrylic acid ester copolymer, epoxy soybean oil
It it is the epoxy soybean oil of liquid under compound, preferably room temperature.
Alkali metal hydroxide mixes with polyvinylidene chloride garbage, can improve the de-of polyvinylidene chloride garbage
Chlorine speed, reduces predecomposition and carbonization time in step (b) and step (c)；Absorb chliorinated polyvinyl chloride to be heated simultaneously
Time produce HCl and generate water, the water of generation at high temperature gasify after in carbonated material produce micro-bubble, formed micro-
The carbonated material of hole foaming, and the structure of the microporous foam formed improves absorption polyvinylidene chloride garbage and is heated and is produced
The efficiency of raw HCl, promotes the dechlorination rate of polyvinylidene chloride garbage, decreases HCl environmental pollution and sets
Standby corrosion.Therefore, alkaline metal oxide of the present invention is KOH, NaOH, Ca (OH)2、Mg(OH)2In
The mixture of one or more, preferably Ca (OH)2、Mg(OH)2In one or both mixture, alkali metal hydrogen
Oxide consumption is 3-8 part.
In twin screw extrusion, on the one hand by each component material mix homogeneously, on the other hand mixture is carried out pre-point
Solve, it is therefore desirable to certain extrusion temperature and residence time of material, extrusion temperature should meet polyvinylidene chloride garbage with
Plasticizer can sufficiently fusion plastification and mixing, but the highest meeting of temperature causes substantial amounts of HCl to produce, and then corrosion twin screw
Extruder, therefore described twin-screw extrusion temperature is 170～200 DEG C, and residence time of material is also to ensure that poly-inclined two chloroethenes
Alkene garbage and plasticizer, alkaline metal oxide can sufficiently fusion plastification and a key factor mixing, and alkali is golden
Belong to hydroxide dispersibility in material and also determine the ability of the produced HCl of its absorption step (b).The time of staying is too
Short, chliorinated polyvinyl chloride and methacrylate copolymer, alkali metal hydroxide can not abundant fusion plastification and mixing,
The time of staying is oversize, and energy consumption is high, and efficiency is low.Therefore in the present invention, the material time of staying in double screw extruder is
15-25 minute.
The purpose of step (b) is that granulation material step (a) formed carries out carbonization.This step is at noble gas
Under the conditions of, carry out two step pyrolysis.Wherein first step thermal decomposition is mainly by gathering in polyvinylidene chloride garbage
Vinylidene chloride carries out preliminary thermal decomposition, and the plasticizer added in step (a) carries out thermal decomposition removal；Second
The polyvinylidene chloride that step thermal decomposition will be decomposed in polyvinylidene chloride garbage further so that polyvinylidene chloride molecule
There is complicated decomposition polycondensation reaction, then in speed of necessarily lowering the temperature in interior and intermolecular group generation bridged bond, free radical and aromatic ring
Carbonated material structure is preliminarily formed under rate.
In step (b) of the present invention, under pyrolytic conditions, the polyvinylidene chloride in polyvinylidene chloride garbage takes off
Chlorine decomposes, forms double bond, Diels-Alder reaction occurs, forms phenyl ring framing structure.For forming carbonization skeleton, need
At noble gas N2Or/and tentatively heat up in Ar atmosphere, and the principal element affecting charred effect be heating rate,
Carbonization temperature and constant temperature time, during this, heating rate is too fast, and cracking reaction can be caused the rapidest；Carbonization temperature is too
Height, constant temperature time is oversize, the most easily makes reaction raw materials form closed pore in degradation process, and then makes char-forming material productivity
Decline, affect average pore size and the specific surface area size of porous carbon materials, cause porous carbon materials performance the best.The present invention
Porous carbon materials is prepared for primary raw material with polyvinylidene chloride garbage, former containing substantial amounts of chlorine in polyvinylidene chloride
Son, and heating rate, carbonization temperature and constant temperature time are to preferably abjection chlorine atom, form double bond further, occur
Diels-Alder react, formed phenyl ring framing structure, simultaneously to the plasticizer degraded as early as possible in polyvinylidene chloride garbage,
The plasticizer added in lubricant, antioxidant and step (a) has an impact.First step heating rate wants very fast, temperature
Should can substantially degrade above-mentioned substance and polyvinylidene chloride can preliminarily form phenyl ring framing structure temperature range and
In time.Therefore, in the present invention, first step intensification selects to be risen by 25 DEG C with heating rate 5～10 DEG C/min with heating rate
Warm to 400～500 DEG C, constant temperature 1～2h.
Preliminarily form char-forming material skeleton owing to previous step heats up, for saving the energy, removed polyvinylidene chloride and discard
The plasticizer added in plasticizer, lubricant, the additive such as antioxidant and the step (a) added in thing, simultaneously
Make the more preferable carbonization of granulation material, therefore in second step temperature-rise period, improve reaction rate, increase reaction temperature, with
Heating rate 10～15 DEG C/min is warming up to 700～800 DEG C, constant temperature 2～3h.
Polyvinylidene chloride garbage hardness is relatively low, after forming carbonated material in temperature-fall period, and can forming part aperture
Shrinking, rate of temperature fall is too fast so that carbonated material skeleton is formed comparatively fast, is unfavorable for preparing the carbonization material of high-specific surface area
Material, is also unfavorable for the carrying out of next step carbon laydown of carbonated material；And rate of temperature fall is too slow, carbonated material skeleton shape can be made
Become too slow, be easily caused carbonated material and form closed pore phenomenon, be also unfavorable for preparing the carbonated material of high-specific surface area, because of
It is 10～20 DEG C/min that this present invention chooses rate of temperature fall.
The carbonated material that the aperture that step (b) is formed by step (c) is big, pore-size distribution is uneven immerses and can produce therewith
In the phenolic resin alcoholic solution of carbon laydown reaction, and then regulate aperture and the pore-size distribution of porous carbon materials.Mainly pass through
Under inert gas conditions, carrying out two step thermal decomposition processes, wherein first step thermal decomposition is main by carbonated material and phenolic resin
Carry out Diels-Alder initial reaction, and under certain rate of temperature fall, preliminarily form porous carbon materials structure, decompose volatilization not
The micromolecular compounds such as the alcohol reacted with carbonated material；Second step thermal decomposition will carry out Diels-Alder reaction, shape further
Become stable molecule structure, and under certain rate of temperature fall, form porous carbon materials structure.
It is relatively big that porous carbon materials after carbonization has aperture, and the problem such as pore-size distribution is wider, affects the property of porous carbon materials
Can and apply.For controlling aperture and the even aperture distribution of porous carbon materials, it is ensured that the stable performance of porous carbon materials,
Material after carbonization is regulated and controled by the present invention, chooses easily and the phenolic resin alcoholic solution of carbonated material infiltration, described phenol
Urea formaldehyde alcoholic solution be the one in phenolic resin methanol solution, phenolic resin ethanol solution, phenolic resin butanol solution or
Several mixture, phenolic resin alcoholic solution is the solution that phenolic resin is dissolved in formed in alcoholic solvent.Phenolic resin alcohol is molten
Liquid excessive concentration can make viscosity big, is unfavorable for that in phenolic resin alcoholic solution infiltration carbonated material micropore, solution concentration is too low
Quantity of solvent can be made too big, increase process costs, the difficulty of solvent volatilization simultaneously reclaims, and easily pollutes environment, therefore, the present invention
The concentration of middle phenolic resin alcoholic solution is preferably 5-20wt.%, and infiltrating time is 1-2h.Because of poly-inclined two in step (b)
Vinyl chloride, under suitable rate of temperature fall, has basically formed skeleton, and therefore, the first step in this step heats up with the speed that heats up
Rate 10-15 DEG C/min starts to warm up to 500-600 DEG C at 25 DEG C, constant temperature 1-2h so that phenolic resin alcoholic solution and step
Suddenly the carbonated material that (b) is prepared carries out preliminary reaction.In second time temperature-rise period, for making phenolic resin alcoholic solution
The carbonated material prepared with step (b) further reacts, and is formed without substantial amounts of little molecule and comes off, and heat up speed
Rate elects 2.5-5 DEG C/min as；For making molecule form heat-staple structure, exist without unstable end-group, it is to avoid affect porous carbon
The application of material, selects to be warming up to 850-900 DEG C, constant temperature 2-3h；For reducing the aperture of porous carbon materials, increase and compare table
Area, selects the cooling rate of 5-10 DEG C/min to be down to 25 DEG C, forms porous carbon materials.
Compared with prior art, the invention have the advantages that
1, low cost, good in economic efficiency, the present invention utilizes polyvinylidene chloride scrap concrete recycling preparation added value
Much higher hole material with carbon element, prepared porous carbon materials function admirable, to stablize, porous carbon materials average pore size is
50-500nm, specific surface area is 600-1500m2/ g, can be used for space division separation, hydrogen storage, gas separation, CO2Catch
Field, economic benefits are the most notable；
2, by composition of raw materials, process step and the optimization of parameter, solve prior art and use polyvinylidene chloride system
The standby porous carbon materials structure obtained there is unstable chlorine atom, is easily generated closed pore phenomenon, it is difficult to control aperture and compare table
Area, and then cause performance and the affected problem of stability of porous carbon materials；
3, technique is simple, environmental protection, and the processing method of the present invention is effectively increased the place of polyvinylidene chloride garbage
Reason efficiency, decreases the pollution to working environment of toxic and harmful HCl in processing procedure and the corrosion of equipment, reduces
Heat decomposition temperature and heat treatment time, reduce energy consumption, solves the environmental pollution and consumption using direct burning disposal to cause
The problem that energy is high.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further detailed, but the invention is not limited in described enforcement
Example.
The performance parameter of the porous carbon materials prepared in the embodiment of the present invention is determined by the following procedure:
Average pore size and specific surface area use the ASAP2010C type nitrogen adsorption desorption of Micromeritics company
Analysis-e/or determining, with nitrogen as adsorbate, measures under liquid nitrogen temperature (77K).
Embodiment 1
Weigh the polyvinylidene chloride garbage 42.5kg after pulverizing, KOH4kg, methyl methacrylate/acrylic acid ester
Copolymer 3.5kg, mixes after 15min under 200rpm rotating speed, through draw ratio 35:1 double screw extruder (producer:
Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, set the mixing section temperature of double screw extruder as 170 DEG C, mould
Changing section temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C, controls the charging rate of material, makes
The material time of staying in double screw extruder is 15 minutes, obtains granulation material.The granulation material obtained is put into baking oven
In, at noble gas N2In atmosphere, start to warm up to 400 DEG C by 25 DEG C with 5 DEG C/min of heating rate, constant temperature 1h, then
Being warming up to 700 DEG C with 10 DEG C/min of heating rate, constant temperature 2h carries out carbonization, is then cooled to 10 DEG C/min of rate of temperature fall
25 DEG C, form carbonated material.The carbonated material formed is immersed in 5wt.% phenolic resin methanol solution and takes out after 1h, put
Enter in baking oven, at noble gas N2In atmosphere, start to warm up to 500 DEG C by 25 DEG C with 10 DEG C/min of heating rate, constant temperature
1h, then it is warming up to 850 DEG C with 2.5 DEG C/min of heating rate, constant temperature 2h, then it is cooled to 25 DEG C with 5 DEG C/min of rate of temperature fall,
Form porous carbon materials.Porous carbon materials average pore size is 50nm, and specific surface area is 1500m2/g。
Embodiment 2
Weighing polyvinylidene chloride garbage 44kg, NaOH2kg after pulverizing, epoxy soybean oil 2kg, at 300rpm
After mixing 15min under rotating speed, through the double screw extruder (producer: the Qingdao limited public affairs of Kechuang plastics machinery of draw ratio 35:1
Department) extruding pelletization, sets the mixing section temperature of double screw extruder as 170 DEG C, fluxing zone temperature is 190 DEG C, compresses
Duan Wendu is 200 DEG C, and head temperature is 180 DEG C, controls the charging rate of material, makes material in double screw extruder
The time of staying be 16 minutes, obtain granulation material.The granulation material obtained is put in baking oven, in noble gas Ar atmosphere
In, start to warm up to 450 DEG C by 25 DEG C with 7.5 DEG C/min of heating rate, constant temperature 1.5h, then with the 12.5 DEG C/min of speed that heats up
Being warming up to 750 DEG C, constant temperature 2.5h carries out carbonization, is then cooled to 25 DEG C with 17.5 DEG C/min of rate of temperature fall, forms carbonization
Material.The carbonated material formed is immersed in 10wt.% phenolic resin ethanol solution and takes out after 1.5h, put in baking oven,
In noble gas Ar atmosphere, start to warm up to 550 DEG C by 25 DEG C with 12.5 DEG C/min of heating rate, constant temperature 1.5h, then
It is warming up to 875 DEG C with 3.5 DEG C/min of heating rate, constant temperature 2.5h, then it is cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall,
Form porous carbon materials.Porous carbon materials average pore size is 500nm, and specific surface area is 600m2/g。
Embodiment 3
Weigh polyvinylidene chloride garbage 47.5kg, Ca (OH) after pulverizing22kg, methyl methacrylate/acrylic acid
Ester copolymer 0.75kg, epoxy soybean oil 0.75kg, after mixing 5min under 400rpm rotating speed, through draw ratio 35:1
Double screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, sets the mixed of double screw extruder
Closing section temperature is 170 DEG C, and fluxing zone temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C, control
The charging rate of material processed, making the material time of staying in double screw extruder is 17 minutes, obtains granulation material.Will
The granulation material obtained is put in baking oven, at noble gas N2In/Ar mixed gas atmosphere, with 10 DEG C/min of heating rate by
25 DEG C start to warm up to 500 DEG C, constant temperature 2h, then are warming up to 800 DEG C with 15 DEG C/min of heating rate, and constant temperature 3h carries out charcoal
Change, be then cooled to 25 DEG C with 20 DEG C/min of rate of temperature fall, form carbonated material.The carbonated material formed is immersed
12.5wt.% phenolic resin butanol solution takes out after 2h, puts in baking oven, at noble gas N2/ Ar mixed gas atmosphere
In, start to warm up to 600 DEG C by 25 DEG C with 15 DEG C/min of heating rate, constant temperature 2h, then with heating rate 5 DEG C/min liter
Warm to 900 DEG C, constant temperature 3h, then it is cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous
Material with carbon element average pore size is 300nm, and specific surface area is 850m2/g。
Embodiment 4
Weigh polyvinylidene chloride garbage 42.5kg, Mg (OH) after pulverizing24kg, methyl methacrylate/the third
Olefin(e) acid ester copolymer 3.5kg, after mixing 10min under 300rpm rotating speed, through the double screw extruder (factory of draw ratio 35:1
Family: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, control the charging rate of material, set double screw extruder
Mixing section temperature be 170 DEG C, fluxing zone temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C,
Making the material time of staying in double screw extruder is 18 minutes, obtains granulation material.The granulation material obtained is put into baking
In case, at noble gas N2In/Ar mixed gas atmosphere, start to warm up to 450 DEG C by 25 DEG C with 5 DEG C/min of heating rate,
Constant temperature 2h, then it is warming up to 700 DEG C with 12.5 DEG C/min of heating rate, constant temperature 2.5h carries out carbonization, then with rate of temperature fall
10 DEG C/min is cooled to 25 DEG C, forms carbonated material.The carbonated material formed is immersed 20wt.% phenolic resin methanol molten
Liquid takes out after 1.75h, puts in baking oven, at noble gas N2In/Ar mixed gas atmosphere, with heating rate
12.5 DEG C/min is started to warm up to 500 DEG C by 25 DEG C, constant temperature 2h, then is warming up to 850 DEG C with 4 DEG C/min of heating rate, permanent
Temperature 2.5h, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms porous carbon materials.The average hole of porous carbon materials
Footpath is 148nm, and specific surface area is 980m2/g。
Embodiment 5
Weigh polyvinylidene chloride garbage 45kg, Ca (OH) after pulverizing21kg, Mg (OH)21kg, epoxy is big
Oleum Glycines 2kg, after mixing 15min under 200rpm rotating speed, through the double screw extruder (producer: Qingdao of draw ratio 35:1
Kechuang plastics machinery company limited) extruding pelletization, set the mixing section temperature of double screw extruder as 175 DEG C, fluxing zone
Temperature is 195 DEG C, and compression section temperature is 200 DEG C, and head temperature is 185 DEG C, controls the charging rate of material, makes material
The time of staying in double screw extruder is 19 minutes, obtains granulation material.The granulation material obtained is put in baking oven,
In noble gas Ar atmosphere, start to warm up to 400 DEG C by 25 DEG C with 7.5 DEG C/min of heating rate, constant temperature 1.5h, then
To heat up, 15 DEG C/min of speed is warming up to 750 DEG C, and constant temperature 2h carries out carbonization, is then cooled to 17.5 DEG C/min of rate of temperature fall
25 DEG C, form carbonated material.The carbonated material formed is immersed in 20wt.% phenolic resin ethanol solution and takes out after 1.5h,
Put in baking oven, in noble gas Ar atmosphere, started to warm up to 550 DEG C by 25 DEG C with 15 DEG C/min of heating rate, permanent
Temperature 1h, then it is warming up to 900 DEG C with 3.5 DEG C/min of heating rate, constant temperature 2.5h, then lowers the temperature with 5 DEG C/min of rate of temperature fall
To 25 DEG C, form porous carbon materials.Porous carbon materials average pore size is 125nm, and specific surface area is 1120m2/g。
Embodiment 6
Weigh polyvinylidene chloride garbage 47.5kg, Ca (OH) after pulverizing22kg, methyl methacrylate/acrylic acid
Ester copolymer 0.75kg, epoxy soybean oil 0.75kg, after mixing 10min under 400rpm rotating speed, through draw ratio 35:1
Double screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, set double screw extruder
Mixing section temperature is 170 DEG C, and fluxing zone temperature is 185 DEG C, and compression section temperature is 200 DEG C, and head temperature is 190 DEG C,
Controlling the charging rate of material, making the material time of staying in double screw extruder is 20 minutes, obtains granulation material.
The granulation material obtained is put in baking oven, at noble gas N2In atmosphere, with 10 DEG C/min of heating rate by 25 DEG C
It is warming up to 500 DEG C, constant temperature 1h, then it is warming up to 800 DEG C with 10 DEG C/min of heating rate, constant temperature 3h carries out carbonization, then
It is cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material formed is immersed 17.5wt.% phenol
Urea formaldehyde ethanol solution takes out after 1.75h, puts in baking oven, at noble gas N2In atmosphere, with heating rate
10 DEG C/min is started to warm up to 600 DEG C by 25 DEG C, constant temperature 1.5h, then is warming up to 875 DEG C with 3.5 DEG C/min of heating rate,
Constant temperature 3h, is then cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall, forms porous carbon materials.The average hole of porous carbon materials
Footpath is 98nm, and specific surface area is 1430m2/g。
Embodiment 7
Weigh the polyvinylidene chloride garbage 46kg after pulverizing, KOH1.5kg, Ca (OH)21kg, methacrylic acid
Methyl ester/acrylate copolymer 1kg, epoxy soybean oil 1kg, after mixing 17min under 200rpm rotating speed, through draw ratio
Double screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of 35:1, sets twin-screw extrusion
The mixing section temperature of machine is 170 DEG C, and fluxing zone temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C,
Controlling the charging rate of material, making the material time of staying in double screw extruder is 21 minutes, obtains granulation material.
The granulation material obtained is put in baking oven, in noble gas Ar atmosphere, with 7.5 DEG C/min of heating rate by 25 DEG C
It is warming up to 400 DEG C, constant temperature 1.5h, then it is warming up to 750 DEG C with the 15 DEG C/min of speed that heats up, constant temperature 2h carries out carbonization, then
It is cooled to 25 DEG C with 15 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material formed is immersed 10wt.% phenolic aldehyde
Resin ethanol solution takes out after 1h, puts in baking oven, in noble gas Ar atmosphere, with 15 DEG C/min of heating rate
Started to warm up to 550 DEG C by 25 DEG C, constant temperature 1h, then be warming up to 900 DEG C with 5 DEG C/min of heating rate, constant temperature 2.5h,
Then it is cooled to 25 DEG C with 5 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous carbon materials average pore size is 177nm,
Specific surface area is 920m2/g。
Embodiment 8
Weigh polyvinylidene chloride garbage 42.5kg, Mg (OH) after pulverizing21kg, Ca (OH)21.5kg, KOH1kg,
Methyl methacrylate/acrylic acid ester copolymer 2.5kg, after mixing 15min under 400rpm rotating speed, through draw ratio 35:1
Double screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, sets the mixed of double screw extruder
Closing section temperature is 170 DEG C, and fluxing zone temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C, control
The charging rate of material processed, making the material time of staying in double screw extruder is 22 minutes, obtains granulation material.Will
The granulation material obtained is put in baking oven, at noble gas N2In atmosphere, rise by 25 DEG C with 10 DEG C/min of heating rate
Temperature is to 500 DEG C, and constant temperature 1h, then be warming up to 800 DEG C with 10 DEG C/min of heating rate, constant temperature 3h carry out carbonization, then with
20 DEG C/min of rate of temperature fall is cooled to 25 DEG C, forms carbonated material.The carbonated material formed is immersed 7.5wt.% phenolic aldehyde tree
Fat ethanol solution takes out after 2h, puts in baking oven, at noble gas N2In atmosphere, with 10 DEG C/min of heating rate by
25 DEG C start to warm up to 600 DEG C, constant temperature 1.5h, then are warming up to 875 DEG C with 2.5 DEG C/min of heating rate, constant temperature 3h, so
After be cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall, formed porous carbon materials.Porous carbon materials average pore size is 385nm,
Specific surface area is 780m2/g。
Embodiment 9
Weigh the polyvinylidene chloride garbage 47kg after pulverizing, KOH0.5kg, NaOH0.5kg, Ca (OH)20.5kg,
Methyl methacrylate/acrylic acid ester copolymer 1kg, after mixing 10min under 400rpm rotating speed, through draw ratio 35:1
Double screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization, set double screw extruder
Mixing section temperature is 170 DEG C, and fluxing zone temperature is 190 DEG C, and compression section temperature is 200 DEG C, and head temperature is 180 DEG C,
Controlling the charging rate of material, making the material time of staying in double screw extruder is 24 minutes, obtains granulation material.
The granulation material obtained is put in baking oven, in noble gas Ar atmosphere, with 7.5 DEG C/min of heating rate by 25 DEG C
It is warming up to 450 DEG C, constant temperature 1.5h, then it is warming up to 750 DEG C with the 12.5 DEG C/min of speed that heats up, constant temperature 2.5h carries out carbonization,
Then it is cooled to 25 DEG C with 12.5 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material formed is immersed 15wt.%
Phenolic resin methanol/ethanol (methanol is 1:1 with the mol ratio of ethanol) solution takes out after 1.5h, puts in baking oven,
In noble gas Ar atmosphere, start to warm up to 500 DEG C by 25 DEG C with 12.5 DEG C/min of heating rate, constant temperature 1.5h, then with
3.5 DEG C/min of heating rate is warming up to 875 DEG C, constant temperature 2.5h, is then cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall,
Form porous carbon materials.Porous carbon materials average pore size is 417nm, and specific surface area is 740m2/g。
Embodiment 10
Weigh polyvinylidene chloride garbage 42.5kg, Ca (OH) after pulverizing23kg, epoxy soybean oil 3kg, at 300rpm
After mixing 20min under rotating speed, through the double screw extruder (producer: the Qingdao limited public affairs of Kechuang plastics machinery of draw ratio 35:1
Department) extruding pelletization, sets the mixing section temperature of double screw extruder as 170 DEG C, fluxing zone temperature is 190 DEG C, compresses
Duan Wendu is 200 DEG C, and head temperature is 180 DEG C, controls the charging rate of material, makes material in double screw extruder
The time of staying be 25 minutes, obtain granulation material.The granulation material obtained is put in baking oven, at noble gas N2Atmosphere
In, start to warm up to 400 DEG C by 25 DEG C with 5 DEG C/min of heating rate, constant temperature 1h, then with heating rate 10 DEG C/min liter
Temperature is to 700 DEG C, and constant temperature 2h carries out carbonization, is then cooled to 25 DEG C with 15 DEG C/min of rate of temperature fall, forms carbonated material.
The carbonated material formed is immersed in 5wt.% phenolic resin ethanol/butanol (ethanol is 1:1 with the mol ratio of butanol) solution
Take out after 1.25h, put in baking oven, at noble gas N2In atmosphere, rise by 25 DEG C with 10 DEG C/min of heating rate
Warm to 500 DEG C, constant temperature 1.5h, then it is warming up to 875 DEG C with 2.5 DEG C/min of heating rate, constant temperature 2h, then with speed of lowering the temperature
7.5 DEG C/min of rate is cooled to 25 DEG C, forms porous carbon materials.Porous carbon materials average pore size is 494nm, specific surface area
For 620m2/g。
Claims (7)
1. the method for a polyvinylidene chloride scrap concrete recycling, it is characterised in that comprise the following steps:
(a) by weight, will pulverize after polyvinylidene chloride garbage 85～95 parts, alkali metal hydroxide
3～8 parts, plasticizer 2～7 parts, under 200～400rpm rotating speeds after stirring mixing, through double spiral shells at a temperature of 170～200 DEG C
Bar extruder extruding pelletization, obtains granulation material；
B granulation material that step (a) is obtained by () is in atmosphere of inert gases, with heating rate 5～10 DEG C/min by 25 DEG C
It is warming up to 400～500 DEG C, constant temperature 1～2h, then it is warming up to 700～800 DEG C with heating rate 10～15 DEG C/min, constant temperature 2～3h
Carry out carbonization, be then down to 25 DEG C with the rate of temperature fall of 10～20 DEG C/min, obtain carbonated material；
C carbonated material that step (b) is obtained by () takes out, at noble gas after immersing in phenolic resin alcoholic solution 1～2h
In atmosphere, it is warming up to 500～600 DEG C with heating rate 10～15 DEG C/min by 25 DEG C, constant temperature 1～2h, then with heating rate
2.5～5 DEG C/min is warming up to 850～900 DEG C, constant temperature 2～3h, is then down to 25 DEG C with the rate of temperature fall of 5～10 DEG C/min,
Obtain porous carbon materials.
The method of polyvinylidene chloride scrap concrete the most according to claim 1 recycling, it is characterised in that step
Suddenly the alkali metal hydroxide described in (a) is KOH, NaOH, Ca (OH)2、Mg(OH)2In one or more
Mixture.
The method of polyvinylidene chloride scrap concrete the most according to claim 1 recycling, it is characterised in that step
Suddenly one or both during the plasticizer described in (a) is methyl methacrylate/acrylic acid ester copolymer, epoxy soybean oil
Mixture.
The method of polyvinylidene chloride scrap concrete the most according to claim 1 recycling, it is characterised in that step
Suddenly during extruding pelletization described in (a), the material time of staying in double screw extruder is 15-25 minute.
The method of polyvinylidene chloride scrap concrete the most according to claim 1 recycling, it is characterised in that step
Suddenly the phenolic resin alcoholic solution described in (c) is phenolic resin methanol solution, phenolic resin ethanol solution, phenolic resin fourth
The mixture of one or more in alcoholic solution.
The method of polyvinylidene chloride scrap concrete the most according to claim 5 recycling, it is characterised in that institute
The phenolic resin alcoholic solution concentration stated is 5～20wt.%.
The method of polyvinylidene chloride scrap concrete the most according to claim 1 recycling, it is characterised in that institute
The porous carbon blanking aperture stated is 50-500nm, and specific surface area is 600-1500m2/g。
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| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN103183345A (en) * | 2011-12-28 | 2013-07-03 | 大连理工大学 | Method for preparation of nitrogen doped activated carbon from chlorine-containing organic polymer waste |
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| CN101062770A (en) * | 2007-05-23 | 2007-10-31 | 华东理工大学 | Spherical activated charcoal having high-ratio surface area and preparation method thereof |
| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN103183345A (en) * | 2011-12-28 | 2013-07-03 | 大连理工大学 | Method for preparation of nitrogen doped activated carbon from chlorine-containing organic polymer waste |
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