CN104192822A - Method for recycling lyvinylidene chloride waste - Google Patents
Method for recycling lyvinylidene chloride waste Download PDFInfo
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- CN104192822A CN104192822A CN201410354557.5A CN201410354557A CN104192822A CN 104192822 A CN104192822 A CN 104192822A CN 201410354557 A CN201410354557 A CN 201410354557A CN 104192822 A CN104192822 A CN 104192822A
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Abstract
The invention discloses a method for recycling lyvinylidene chloride waste. The method comprises the following steps: (a) proportioning pulverized lyvinylidene chloride waste, alkaline metal hydroxide and a plasticizer in parts by weight and then stirring and mixing, and extruding and pelletizing at a temperature of 170-200 DEG C; (b) heating the pelletized material in an inert gas atmosphere at two different heating rates to 700-800 DEG C from 25 DEG C in two steps, and cooling to 25 DEG C at the rate of 10-20 DEG C/min to obtain carbonized material; and (c) immersing the carbonized materials into an alcohol solution of phenolic resin for 1-2 hours, and heating the carbonized material to 850-900 DEG C from 25 DEG C at two different heating rates in two steps, and cooling to 25 DEG C at the rate of 5-10 DEG C/min to obtain a porous carbon material. The method is simple in process, friendly to the environment, low in cost and good in economic benefits.
Description
Technical field
The present invention relates to the method for waste recycling, specific to the method that relates to the recycling of a kind of polyvinylidene dichloride waste.
Background technology
Polyvinylidene dichloride is widely used in the fields such as food product pack, chinampa, wig, netting twine at present.In the processing of polyvinylidene dichloride and use procedure, unavoidably can produce the Litter the like waste after a large amount of waste materials, scrap stock and use.Because polyvinylidene dichloride at high temperature easily decomposes, cause polyvinylidene dichloride waste to reclaim processing difficulties again; Adopt directly and burn and cause environmental pollution, and it is high to consume energy.
Porous carbon materials is the novel nonpolar carbonaceous sorbent material of one growing up the sixties in 20th century.Porous carbon materials even aperture distribution; have very high chemical stability and gas-selectively, at present porous carbon materials has been widely used in the every field such as environment protection, chemical industry, petroleum industry, food-processing, hydrometallurgy, medicine are refining, militarization protection.
The raw material of preparing porous carbon materials is extensive, mainly include machine high molecular polymer (Saran resin (polyvinylidene dichloride), resol etc.), various coal and coal-based derivative (brown coal, bituminous coal, hard coal etc.), biomass (timber, shell, bagasse etc.), oil by product (petroleum residue, refinery coke, petroleum pitch etc.), the difference of raw material makes to prepare porous carbon materials technique difference, and the performance of the porous carbon materials obtaining is also different.In addition, the existing method cost of preparing porous carbon materials is higher.Therefore find a kind of raw material cheap and easy to get, the preparation method of the porous carbon materials that the product performance that prepare are stable, is to need the urgent problems that solve.
Under certain condition, dechlorination, forms two keys to polyvinylidene dichloride, Diels-Alder occurs and be reacted into ring, can obtain porous carbon materials product.Therefore, utilize polyvinylidene dichloride waste to prepare porous carbon materials, can effectively process polyvinylidene dichloride waste, can turn waste into wealth again, obtain the porous carbon materials of high added value.But in polyvinylidene dichloride waste, contain the multiple processing aid adding in polyvinylidene dichloride processing preparation process, as softening agent, lubricant, oxidation inhibitor etc., polyvinylidene dichloride is according to synthesis technique difference in addition, the polyvinylidene dichloride product composition complexity obtaining, comprise the homopolymer of vinylidene chloride or the multipolymer of vinylidene chloride and acrylate or chloroethylene copolymer, therefore the stable porous carbon materials of product performance that utilizes polyvinylidene dichloride waste to prepare, difficulty is very big, need to overcome composition of raw materials, many technical barriers such as preparation process and parameter.At present, utilize polyvinylidene dichloride waste to prepare porous carbon materials and also rarely have report.
Summary of the invention
The technical problem to be solved in the present invention is the defect that overcomes prior art, provides that a kind of technique is simple, environmental protection, cost be low, the method for good in economic efficiency polyvinylidene dichloride waste recycling.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: the method for a kind of polyvinylidene dichloride waste recycling, comprises the following steps:
(a) by weight, by 85～95 parts, the polyvinylidene dichloride waste after pulverizing, 3～8 parts of alkali metal hydroxides, 2～7 parts, softening agent, after being uniformly mixed, at 170～200 DEG C of temperature, through twin screw extruder extruding pelletization, obtain granulation material under 200～400rpm rotating speed;
(b) granulation material step (a) being obtained is in atmosphere of inert gases, be warming up to 400～500 DEG C with 5～10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1～2h, be warming up to 700～800 DEG C with 10～15 DEG C/min of temperature rise rate again, constant temperature 2～3h carries out charing, then be 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 immerses in resol alcoholic solution and takes out after 1～2h, in atmosphere of inert gases, be warming up to 500～600 DEG C with 10～15 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1～2h, be warming up to 850～900 DEG C with 2.5～5 DEG C/min of temperature rise rate again, constant temperature 2～3h, is then down to 25 DEG C with the rate of temperature fall of 5～10 DEG C/min, obtains porous carbon materials.
As the preferred embodiment of the present invention, the described alkali metal hydroxide of step (a) is KOH, NaOH, Ca (OH)
2, Mg (OH)
2in one or more mixture.
As the preferred embodiment of the present invention, the described softening agent of step (a) is one or both the mixture in methyl methacrylate/acrylic acid ester copolymer, epoxy soybean oil.
As the preferred embodiment of the present invention, when the described extruding pelletization of step (a), the residence time of material in twin screw extruder is 15-25 minute.
As the preferred embodiment of the present invention, the described resol alcoholic solution of step (c) is one or more the mixture in resol methanol solution, resol ethanolic soln, resol butanol solution.
As the preferred embodiment of the present invention, described resol 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 600-1500m
2/ g.
Polyvinylidene dichloride waste of the present invention, in the polyvinylidene dichloride course of processing or use Litter after the scrap stock, waste material, use that produce etc., shatters polyvinylidene dichloride waste rear as raw material for standby.
In the present invention, by step (a), a certain proportion of polyvinylidene dichloride waste, alkali metal hydroxide and softening agent are mixed, simultaneously in melting process, there is preliminary decomposition in polyvinylidene dichloride waste, and then obtains the required granulation material of step (b).
The mechanical property of the proportioning of raw material to porous carbon materials and preparation condition and step have considerable influence, and the proportioning of reasonable preparation raw material is the committed step that obtains high performance porous carbon materials.Polyvinylidene dichloride has added multiple processing aid in preparation process, as softening agent, lubricant, oxidation inhibitor etc., polyvinylidene dichloride waste is in reprocessing process, only need to add again comparatively a small amount of softening agent so that extrusion moulding smoothly in twin screw extrusion, for reducing porous carbon materials preparation cost, the plasticizer consumption using in the present invention is preferably 2-7 part.For ensureing that the softening agent and the polyvinylidene dichloride waste that add have good consistency, avoid producing in raw mixture phase-splitting, and then affect the aperture homogeneity of porous carbon materials, softening agent is one or both the mixture in methyl methacrylate/acrylic acid ester copolymer, epoxy soybean oil, under normal temperature, is preferably liquid epoxy soybean oil.
Alkali metal hydroxide mixes with polyvinylidene dichloride waste, can improve the dechlorination rate of polyvinylidene dichloride waste, reduces predecomposition and carbonization time in step (b) and step (c); The HCl producing when absorbing chlorinated polyvinyl chloride simultaneously and being heated also generates water, after at high temperature gasifying, the water generating in carbonated material, produces micro-bubble, form the carbonated material of microporous foam, and the structure of microporous foam forming has improved and has absorbed the be heated efficiency of produced HCl of polyvinylidene dichloride waste, promote the dechlorination rate of polyvinylidene dichloride waste, reduced the corrosion of HCl environmental pollution and equipment.Therefore, alkaline metal oxide of the present invention is KOH, NaOH, Ca (OH)
2, Mg (OH)
2in one or more mixture, preferably Ca (OH)
2, Mg (OH)
2in one or both mixture, alkali metal hydroxide consumption is 3-8 part.
In twin screw extrusion, on the one hand each constituent materials is mixed, on the other hand mixture is carried out to predecomposition, therefore need certain extrusion temperature and residence time of material, extrusion temperature should meet polyvinylidene dichloride waste and softening agent fusion plastification and mixing fully, but the too high meeting of temperature causes a large amount of HCl to produce, and then corrosion twin screw extruder, therefore described twin-screw extrusion temperature is 170～200 DEG C, residence time of material is also to ensure polyvinylidene dichloride waste and softening agent, an important factor of alkaline metal oxide fusion plastification and mixing fully, and the dispersiveness of alkali metal hydroxide in material also determined the ability of its absorption step (b) HCl that produces.The residence time is too short, fully fusion plastification and mixing of chlorinated polyvinyl chloride and alkylmethacrylate polymer, alkali metal hydroxide, and the residence time is oversize, and energy consumption is high, and efficiency is low.Therefore in the present invention, the residence time of material in twin screw extruder is 15-25 minute.
The object of step (b) is that the granulation material that step (a) is formed carries out carbonization.This step is under inert gas conditions, carries out two step pyrolysis.Wherein the first step thermolysis is mainly that the polyvinylidene dichloride in polyvinylidene dichloride waste is carried out to preliminary thermolysis, and the softening agent adding in step (a) is carried out to thermolysis removal; Second step thermolysis is by the polyvinylidene dichloride further decomposing in polyvinylidene dichloride waste, make with intermolecular group generation bridged bond, free radical and aromatic ring, complicated decomposition polycondensation to occur in polyvinylidene dichloride molecule, then under certain rate of temperature fall, beginning to take shape carbonated material structure.
In step of the present invention (b), under pyrolytical condition, the polyvinylidene dichloride in polyvinylidene dichloride waste carries out dechlorination decomposition, forms two keys, and Diels-Alder reaction occurs, and forms phenyl ring skeleton structure.For forming charing skeleton, need to be at rare gas element N
2or/and tentatively heat up in Ar atmosphere, and the principal element that affects charing effect is temperature rise rate, carbonization temperature and constant temperature time, and in this process, temperature rise rate is too fast, can cause scission reaction too quickly; Carbonization temperature is too high, and constant temperature time is oversize, all easily makes reaction raw materials in degradation process, form closed pore, and then char-forming material productive rate is declined, and affects mean pore size and the specific surface area size of porous carbon materials, causes porous carbon materials performance not good.The present invention prepares porous carbon materials taking polyvinylidene dichloride waste as main raw material, in polyvinylidene dichloride, contain a large amount of chlorine atoms, and temperature rise rate, carbonization temperature and constant temperature time are to better deviating from chlorine atom, further form two keys, there is Diels-Alder reaction, form phenyl ring skeleton structure, the softening agent adding is had to impact simultaneously in softening agent, lubricant, oxidation inhibitor and the step (a) of degrading as early as possible in polyvinylidene dichloride waste.It is very fast that the first step temperature rise rate is wanted, and temperature should can begin to take shape the temperature range of phenyl ring skeleton structure and in the time at can substantially degrade above-mentioned substance and polyvinylidene dichloride.Therefore, in the present invention, the first step intensification is selected to be warming up to 400～500 DEG C, constant temperature 1～2h with 5～10 DEG C/min of temperature rise rate by 25 DEG C with temperature rise rate.
Because heating up, previous step begins to take shape char-forming material skeleton, for save energy, remove the softening agent adding in the additives such as the softening agent that adds in polyvinylidene dichloride waste, lubricant, antioxidant and step (a), make the better carbonization of granulation material simultaneously, therefore in second step temperature-rise period, improve speed of reaction, increase temperature of reaction, be warming up to 700～800 DEG C with 10～15 DEG C/min of temperature rise rate, constant temperature 2～3h.
Polyvinylidene dichloride waste hardness is lower, forming after carbonated material in temperature-fall period, can shrink in forming section aperture, rate of temperature fall is too fast, carbonated material skeleton is formed comparatively fast, be unfavorable for preparing the carbonated material of high-specific surface area, be also unfavorable for the carrying out of next step carbon laydown of carbonated material; And rate of temperature fall is too slow, can make carbonated material skeleton form too slow, easily cause carbonated material to form closed pore phenomenon, be also unfavorable for preparing the carbonated material of high-specific surface area, therefore to choose rate of temperature fall be 10～20 DEG C/min in the present invention.
The carbonated material that aperture is large, pore size distribution is uneven that step (c) forms step (b) immerses in the resol alcoholic solution that can produce with it carbon laydown reaction, and then regulates aperture and the pore size distribution of porous carbon materials.Main by under inert gas conditions, carry out two step thermal decomposition processes, wherein the first step thermolysis is mainly carried out Diels-Alder initial reaction by carbonated material and resol, and under certain rate of temperature fall, begin to take shape porous carbon materials structure, the micromolecular compounds such as the alcohol that decomposing volatilizees does not react with carbonated material; Diels-Alder reaction will be further carried out in second step thermolysis, form stable molecule structure, and form porous carbon materials structure under certain rate of temperature fall.
It is larger that porous carbon materials after charing has aperture, and the problem such as pore size distribution is wider, affects performance and the application of porous carbon materials.For controlling aperture and the even aperture distribution of porous carbon materials, ensure the stable performance of porous carbon materials, the present invention regulates and controls the material after charing, choose resol alcoholic solution easy and that carbonated material infiltrates, described resol alcoholic solution is one or more the mixture in resol methanol solution, resol ethanolic soln, resol butanol solution, the solution that resol alcoholic solution forms in alcoholic solvent for resol is dissolved in.Resol alcoholic solution excessive concentration can make viscosity large, be unfavorable for that resol alcoholic solution infiltrates in carbonated material micropore, the too low meeting of strength of solution makes quantity of solvent too large, increase process costs, solvent evaporates is difficult simultaneously reclaims, easily contaminate environment, therefore, in the present invention, the concentration of resol alcoholic solution is preferably 5-20wt.%, and infiltrating time is 1-2h.Because the polyvinylidene dichloride in step (b) is under suitable rate of temperature fall, basically form skeleton, therefore, the first step in this step heats up and at 25 DEG C, starts to be warming up to 500-600 DEG C with temperature rise rate 10-15 DEG C/min, constant temperature 1-2h, makes resol alcoholic solution carry out preliminary reacting with the carbonated material that step (b) makes.In temperature-rise period for the second time, for the carbonated material that resol alcoholic solution and step (b) are made further reacts, come off and do not form a large amount of small molecules, temperature rise rate is elected 2.5-5 DEG C/min as; For making molecule form heat-staple structure, stable end groups exists invariably, avoids affecting the application of porous carbon materials, selects to be warming up to 850-900 DEG C, constant temperature 2-3h; For reducing the aperture of porous carbon materials, increase specific surface area, select the cooling rate of 5-10 DEG C/min to be down to 25 DEG C, form porous carbon materials.
Compared with prior art, the present invention has the following advantages:
1, cost is low, good in economic efficiency, and the present invention utilizes the recycling of polyvinylidene dichloride waste to prepare the much higher hole of added value carbon material, the porous carbon materials excellent property making, stablize, porous carbon materials mean pore size is 50-500nm, and specific surface area is 600-1500m
2/ g, can be used for empty point separation, Chu Qing, gas delivery, CO
2the fields such as seizure, economic benefits are very remarkable;
2, by the optimization of composition of raw materials, treatment step and parameter, solve in the porous carbon materials structure that prior art uses polyvinylidene dichloride to prepare and had a unstable chlorine atom, easily produce closed pore phenomenon, be difficult to control aperture and specific surface area, and then cause performance and the affected problem of stability of porous carbon materials;
3, simple, the environmental protection of technique, treatment process of the present invention has effectively improved the processing efficiency of polyvinylidene dichloride waste, the pollution of toxic and harmful HCl to Working environment and the corrosion of equipment in treating processes are reduced, heat decomposition temperature and heat treatment time are reduced, reduce energy consumption, solved the environmental pollution and the high problem of power consumption that adopt direct burning disposal to cause.
Embodiment
Below in conjunction with specific embodiment, the present invention is further detailed, but the present invention is not limited to described embodiment.
The performance perameter of the porous carbon materials making in the embodiment of the present invention is measured by the following method:
Mean pore size and specific surface area adopt the ASAP2010C type nitrogen adsorption of Micromeritics company---and desorption analysis instrument is measured, taking nitrogen as adsorbate, in the lower mensuration of liquid nitrogen temperature (77K).
Embodiment 1
Take the polyvinylidene dichloride waste 42.5kg after pulverizing, KOH4kg, methyl methacrylate/acrylic acid ester copolymer 3.5kg, under 200rpm rotating speed, mix after 15min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 15 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 400 DEG C with 5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 700 DEG C with 10 DEG C/min of temperature rise rate, constant temperature 2h carries out charing, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 5wt.% resol methanol solution and taken out after 1h, put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 500 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 850 DEG C with 2.5 DEG C/min of temperature rise rate, constant temperature 2h, is then cooled to 25 DEG C with 5 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous carbon materials mean pore size is 50nm, and specific surface area is 1500m
2/ g.
Embodiment 2
Take the polyvinylidene dichloride waste 44kg after pulverizing, NaOH2kg, epoxy soybean oil 2kg, under 300rpm rotating speed, mix after 15min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 16 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 450 DEG C with 7.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, be warming up to 750 DEG C with the 12.5 DEG C/min of speed that heats up again, constant temperature 2.5h carries out charing, is then cooled to 25 DEG C with 17.5 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 10wt.% resol ethanolic soln and taken out after 1.5h, put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 550 DEG C with 12.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, then be warming up to 875 DEG C, constant temperature 2.5h with 3.5 DEG C/min of temperature rise rate, then be cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall, form porous carbon materials.Porous carbon materials mean pore size is 500nm, and specific surface area is 600m
2/ g.
Embodiment 3
Take the polyvinylidene dichloride waste 47.5kg after pulverizing, Ca (OH)
22kg, methyl methacrylate/acrylic acid ester copolymer 0.75kg, epoxy soybean oil 0.75kg, under 400rpm rotating speed, mix after 5min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 17 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in/Ar mixed gas atmosphere, start to be warming up to 500 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 2h, then be warming up to 800 DEG C with 15 DEG C/min of temperature rise rate, constant temperature 3h carries out charing, is then cooled to 25 DEG C with 20 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 12.5wt.% resol butanol solution and taken out after 2h, put into baking oven, at rare gas element N
2in/Ar mixed gas atmosphere, start to be warming up to 600 DEG C with 15 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 2h, then be warming up to 900 DEG C with 5 DEG C/min of temperature rise rate, constant temperature 3h, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous carbon materials mean pore size is 300nm, and specific surface area is 850m
2/ g.
Embodiment 4
Take the polyvinylidene dichloride waste 42.5kg after pulverizing, Mg (OH)
24kg, methyl methacrylate/acrylic acid ester copolymer 3.5kg, under 300rpm rotating speed, mix after 10min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, control the input speed of material, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, making the residence time of material in twin screw extruder is 18 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in/Ar mixed gas atmosphere, start to be warming up to 450 DEG C, constant temperature 2h with 5 DEG C/min of temperature rise rate by 25 DEG C, be warming up to 700 DEG C with 12.5 DEG C/min of temperature rise rate again, constant temperature 2.5h carries out charing, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 20wt.% resol methanol solution and taken out after 1.75h, put into baking oven, at rare gas element N
2in/Ar mixed gas atmosphere, start to be warming up to 500 DEG C with 12.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 2h, then be warming up to 850 DEG C with 4 DEG C/min of temperature rise rate, constant temperature 2.5h, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous carbon materials mean pore size is 148nm, and specific surface area is 980m
2/ g.
Embodiment 5
Take the polyvinylidene dichloride waste 45kg after pulverizing, Ca (OH)
21kg, Mg (OH)
21kg, epoxy soybean oil 2kg, under 200rpm rotating speed, mix after 15min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 175 DEG C, fluxing zone temperature is 195 DEG C, compression section temperature is 200 DEG C, and head temperature is 185 DEG C, controls the input speed of material, making the residence time of material in twin screw extruder is 19 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 400 DEG C with 7.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, be warming up to 750 DEG C with the 15 DEG C/min of speed that heats up again, constant temperature 2h carries out charing, is then cooled to 25 DEG C with 17.5 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 20wt.% resol ethanolic soln and taken out after 1.5h, put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 550 DEG C with 15 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 900 DEG C, constant temperature 2.5h with 3.5 DEG C/min of temperature rise rate, then be cooled to 25 DEG C with 5 DEG C/min of rate of temperature fall, form porous carbon materials.Porous carbon materials mean pore size is 125nm, and specific surface area is 1120m
2/ g.
Embodiment 6
Take the polyvinylidene dichloride waste 47.5kg after pulverizing, Ca (OH)
22kg, methyl methacrylate/acrylic acid ester copolymer 0.75kg, epoxy soybean oil 0.75kg, under 400rpm rotating speed, mix after 10min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 185 DEG C, compression section temperature is 200 DEG C, head temperature is 190 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 20 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 500 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 800 DEG C with 10 DEG C/min of temperature rise rate, constant temperature 3h carries out charing, is then cooled to 25 DEG C with 10 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 17.5wt.% resol ethanolic soln and taken out after 1.75h, put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 600 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, then be warming up to 875 DEG C with 3.5 DEG C/min of temperature rise 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.Porous carbon materials mean pore size is 98nm, and specific surface area is 1430m
2/ g.
Embodiment 7
Take the polyvinylidene dichloride waste 46kg after pulverizing, KOH1.5kg, Ca (OH)
21kg, methyl methacrylate/acrylic acid ester copolymer 1kg, epoxy soybean oil 1kg, under 200rpm rotating speed, mix after 17min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 21 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 400 DEG C with 7.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, be warming up to 750 DEG C with the 15 DEG C/min of speed that heats up again, constant temperature 2h carries out charing, is then cooled to 25 DEG C with 15 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 10wt.% resol ethanolic soln and taken out after 1h, put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 550 DEG C with 15 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 900 DEG C, constant temperature 2.5h with 5 DEG C/min of temperature rise rate, then be cooled to 25 DEG C with 5 DEG C/min of rate of temperature fall, form porous carbon materials.Porous carbon materials mean pore size is 177nm, and specific surface area is 920m
2/ g.
Embodiment 8
Take the polyvinylidene dichloride waste 42.5kg after pulverizing, Mg (OH)
21kg, Ca (OH)
21.5kg, KOH1kg, methyl methacrylate/acrylic acid ester copolymer 2.5kg, under 400rpm rotating speed, mix after 15min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, the input speed of controlling material, making the residence time of material in twin screw extruder is 22 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 500 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 800 DEG C with 10 DEG C/min of temperature rise rate, constant temperature 3h carries out charing, is then cooled to 25 DEG C with 20 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material of formation is immersed in 7.5wt.% resol ethanolic soln and taken out after 2h, put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 600 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, then be warming up to 875 DEG C with 2.5 DEG C/min of temperature rise 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.Porous carbon materials mean pore size is 385nm, and specific surface area is 780m
2/
g.
Embodiment 9
Take the polyvinylidene dichloride waste 47kg after pulverizing, KOH0.5kg, NaOH0.5kg, Ca (OH)
20.5kg, methyl methacrylate/acrylic acid ester copolymer 1kg, under 400rpm rotating speed, mix after 10min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, head temperature is 180 DEG C, control the input speed of material, making the residence time of material in twin screw extruder is 24 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 450 DEG C with 7.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, be warming up to 750 DEG C with the 12.5 DEG C/min of speed that heats up again, constant temperature 2.5h carries out charing, is then cooled to 25 DEG C with 12.5 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material forming is immersed in 15wt.% resol methanol/ethanol (mol ratio of methyl alcohol and ethanol is 1:1) solution and taken out after 1.5h, put into baking oven, in rare gas element Ar atmosphere, start to be warming up to 500 DEG C with 12.5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, then be warming up to 875 DEG C, constant temperature 2.5h with 3.5 DEG C/min of temperature rise rate, then be cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall, form porous carbon materials.Porous carbon materials mean pore size is 417nm, and specific surface area is 740m
2/
g.
Embodiment 10
Take the polyvinylidene dichloride waste 42.5kg after pulverizing, Ca (OH)
23kg, epoxy soybean oil 3kg, under 300rpm rotating speed, mix after 20min, through twin screw extruder (producer: Qingdao Kechuang Plastic Machinery Co., Ltd.) extruding pelletization of length-to-diameter ratio 35:1, the mixing section temperature of setting twin screw extruder is 170 DEG C, fluxing zone temperature is 190 DEG C, compression section temperature is 200 DEG C, and head temperature is 180 DEG C, controls the input speed of material, making the residence time of material in twin screw extruder is 25 minutes, obtains granulation material.The granulation material obtaining is put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 400 DEG C with 5 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1h, then be warming up to 700 DEG C with 10 DEG C/min of temperature rise rate, constant temperature 2h carries out charing, is then cooled to 25 DEG C with 15 DEG C/min of rate of temperature fall, forms carbonated material.The carbonated material forming is immersed in 5wt.% resol ethanol/butanols (mol ratio of ethanol and butanols is 1:1) solution and taken out after 1.25h, put into baking oven, at rare gas element N
2in atmosphere, start to be warming up to 500 DEG C with 10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1.5h, then be warming up to 875 DEG C with 2.5 DEG C/min of temperature rise rate, constant temperature 2h, is then cooled to 25 DEG C with 7.5 DEG C/min of rate of temperature fall, forms porous carbon materials.Porous carbon materials mean pore size is 494nm, and specific surface area is 620m
2/
g.
Claims (7)
1. a method for polyvinylidene dichloride waste recycling, is characterized in that comprising the following steps:
(a) by weight, by 85～95 parts, the polyvinylidene dichloride waste after pulverizing, 3～8 parts of alkali metal hydroxides, 2～7 parts, softening agent, after being uniformly mixed, at 170～200 DEG C of temperature, through twin screw extruder extruding pelletization, obtain granulation material under 200～400rpm rotating speed;
(b) granulation material step (a) being obtained is in atmosphere of inert gases, be warming up to 400～500 DEG C with 5～10 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1～2h, be warming up to 700～800 DEG C with 10～15 DEG C/min of temperature rise rate again, constant temperature 2～3h carries out charing, then be down to 25 DEG C with the rate of temperature fall of 10～20 DEG C/min, obtain carbonated material;
(c) carbonated material step (b) being obtained immerses in resol alcoholic solution and takes out after 1～2h, in atmosphere of inert gases, be warming up to 500～600 DEG C with 10～15 DEG C/min of temperature rise rate by 25 DEG C, constant temperature 1～2h, be warming up to 850～900 DEG C with 2.5～5 DEG C/min of temperature rise rate again, constant temperature 2～3h, is then down to 25 DEG C with the rate of temperature fall of 5～10 DEG C/min, obtains porous carbon materials.
2. the method for polyvinylidene dichloride waste according to claim 1 recycling, is characterized in that the described alkali metal hydroxide of step (a) is KOH, NaOH, Ca (OH)
2, Mg (OH)
2in one or more mixture.
3. the method for polyvinylidene dichloride waste according to claim 1 recycling, is characterized in that the described softening agent of step (a) is one or both the mixture in methyl methacrylate/acrylic acid ester copolymer, epoxy soybean oil.
4. the method for polyvinylidene dichloride waste according to claim 1 recycling, while it is characterized in that the described extruding pelletization of step (a), the residence time of material in twin screw extruder is 15-25 minute.
5. the method for polyvinylidene dichloride waste according to claim 1 recycling, is characterized in that the described resol alcoholic solution of step (c) is one or more the mixture in resol methanol solution, resol ethanolic soln, resol butanol solution.
6. the method for polyvinylidene dichloride waste according to claim 5 recycling, is characterized in that described resol alcoholic solution concentration is 5～20wt.%.
7. the method for polyvinylidene dichloride waste according to claim 1 recycling, is characterized in that described porous carbon blanking aperture is 50-500nm, and specific surface area is 600-1500m
2/ g.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108404334A (en) * | 2018-04-11 | 2018-08-17 | 同济大学 | A method of detoxified halogenated debirs using hydroxide inorganic melt dechlorination |
| CN108404334B (en) * | 2018-04-11 | 2020-11-27 | 同济大学 | Method for dechlorinating and detoxifying halogenated organic waste by using hydroxide inorganic melt |
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