CN109438751A - A kind of Thermal degradation method of halogen plastics - Google Patents

A kind of Thermal degradation method of halogen plastics Download PDF

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CN109438751A
CN109438751A CN201811292207.5A CN201811292207A CN109438751A CN 109438751 A CN109438751 A CN 109438751A CN 201811292207 A CN201811292207 A CN 201811292207A CN 109438751 A CN109438751 A CN 109438751A
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halogen
plastics
thermal degradation
bottle
reaction
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CN109438751B (en
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高建峰
段政
刘艳
郝敏
徐春燕
徐明英
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North University of China
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a kind of Thermal degradation methods of halogen plastics, and using PVC as raw material, using aluminium powder as catalyst, using alchlor and iodine as initiator, in activating solvent system, reaction generates alchlor and Halogen carbon compound under the conditions of 43 ~ 100 DEG C.The invention avoids existing most of halogen plastics to need just to can be carried out under the conditions of 800 DEG C of Pintsch process, and need nitrogen protection more, and product hydrochloric acid has the appearance of the problem of very big corrosion；It can be effectively reduced energy consumption, equipment avoided to corrode；Aluminium powder is converted to aluminum trichloride (anhydrous) after reaction, the problem of halogen plastic degradation hardly possible is not only solved, biggish economic value is more produced by degradative plastics.

Description

A kind of Thermal degradation method of halogen plastics
Technical field
The invention belongs to plastic degradation technical fields, are related to a kind of biodegrading process of halogen plastics, more particularly to one kind The Thermal degradation method of halogen plastics.
Background technique
With the rapid development of plastics industry, plastic product is also widely used in automobile, electric, building and packaging etc. Halogenated flame retardant is then just widely applied in plastics by industry since current most products all require flame retardant rating. But just because of in plastics halogen presence, increase the recovery difficult of halogen-containing waste plastic instead.Because during processing, containing It is poisonous and hazardous containing halogenation that halogen in halogen plastics is readily formed such as this kind of hydrogen halides, halogenated phenols, dioxin and furans Object is closed, environment is not only polluted, corrosion treatment equipment increases processing cost；Once halogen containing organic compound enters liquids and gases The recycling that also will cause these products in product is difficult.Therefore, most plastic garbages can not be degraded or recycle, For people by them together with Other Waste, depths or on-site incineration of the landfill in soot not only cause the wasting of resources, And generate great, irreversible environmental pollution.In recent years, with a large amount of times of halogen plastics in electronic apparatus waste It receives, environmental requirement further increases.Halogen-containing waste plastic dehalogenation becomes the necessary links in reclaiming.
Halogen in halogen plastics is mainly derived from polyvinyl chloride (PVC) and halogen containing flame-retardant, and dehalogenation mode mainly includes Destructive dehalogenation and non-destructive dehalogenation both.Destructive dehalogenation mainly allows plastics itself to decompose come real by some conditions Existing dehalogenation, such as two sections of thermal decomposition method dehalogenations, thermal decomposition absorption dehalogenation and thermal decomposition catalysis this kind of thermal decomposition dehalogenation of dehalogenation；Non-demolition Property dehalogenation be that halogen element is removed under the premise of plastics macromolecular main chain structure is immovable, such as hydrolyze dehalogenation, solvent extraction and Electronation etc..Currently, non-destructive dehalogenation technology is mostly using supercritical technology, cost is high, does not have application also currently Value；Although destructive dehalogenation technology has put into industrial application, dehalogenation effect is not satisfied enough, and has two and great ask Topic, first condition have high temperature (generally requiring 280 DEG C or more), consume energy larger；Second experiment is used with high costs, it is difficult to extensively Using.
Since waste and old halogen plastics have resource and the big characteristic of pollution two simultaneously, how waste and old contain is being recycled The pollution to environment is reduced when halogen plastics, is a great problem and challenge at this stage.Therefore, realize at this stage it is innoxious Dehalogenation is the project of a very worth research.
Summary of the invention
The generally existing reaction temperature for the treatment of process in order to solve halogen plastics in the prior art is high, waste liquid is more, energy consumption is high, To the problem of consersion unit and condition harshness, the invention discloses a kind of Thermal degradation methods of halogen plastics, first use initiator Initiation active metal powder is reacted with halogenated hydrocarbon solvent, anti-with halogen plastics at 43 ~ 100 DEG C after so that metal is become active metal It answers, the halogen captured in halogen plastics makes plastic degradation.
The technical scheme of the present invention is realized as follows:
The invention discloses a kind of Thermal degradation methods of halogen plastics, in normal pressure, open system, using PVC as raw material, with aluminium Powder is catalyst, using alchlor and iodine as initiator, and in activating solvent system, reaction generates three under the conditions of 43 ~ 100 DEG C Aluminium chloride and Halogen carbon compound；Depending on its reaction time is with reaction temperature, usually 20 ~ 80min；It further, will be upper It states reaction raw materials, catalyst, initiator and after the reaction was completed, mixture is distilled to recover liquid, through red under the conditions of 43 ~ 100 DEG C Outer characterization is mainly unreacted carbon tetrachloride.
Remaining solid handles a kind of method and dissolves aluminum trichloride (anhydrous) using dehydrated alcohol, obtains yellow shape filtrate through filtering With black filter residue, dehydrated alcohol repeatedly washs filter residue, and whole filtrates are distilled, and has fraction outflow, predominantly second at 70 ~ 78 DEG C Alcohol stops distillation when having the precipitation of a large amount of yellow crystals in solution, shows that dehydrated alcohol recycles substantially, and cooling obtains anhydrous tri-chlorination The yellow solid of aluminium；Filter residue is dried to 6 ~ 10h at 80 ± 5 DEG C and is contained the Halogen of-C=C- and amorphous carbon containing carbon compound Object.
It is directly to distill that remaining solid, which handles second method, and different temperatures recycles low temperature organic matter (less than 100 DEG C), then Aluminum trichloride (anhydrous) is recycled using higher temperature (100 ~ 150 DEG C) sublimed method, obtains aluminum trichloride (anhydrous) and black filter residue.
Initiator accounts for the mass fraction 0.5 ~ 2% of activating solvent, tri-chlorination in initiator as a preferred implementation manner, Aluminium and iodine quality ratio are 1:1.
Other halogen plastics such as certain polytetrafluoroethylene (PTFE) can also using aluminium powder as catalyst, using alchlor and iodine as initiation Agent carries out Thermal degradation in activating solvent system.
The present invention carries out under cryogenic, and reaction condition is 45 ~ 75 DEG C as a preferred implementation manner,；More Excellently, reaction condition is 58 DEG C.
The activating solvent is halogen small molecule solvent as a preferred implementation manner,；Preferably, the activating solvent For bromoethane and/or carbon tetrachloride；Preferably, the activating solvent is carbon tetrachloride；Further, the PVC and activation are molten 1.5 ~ 15:1 of mass ratio of agent.
Further, containing polyacetylene and contain the amorphous carbon of graphite-structure in the Halogen carbon compound.
The mass ratio of the PVC and aluminium powder is 1 ~ 3:1 as a preferred implementation manner,；Preferably, the PVC and aluminium The mass ratio of powder is 3:2.
Aluminum trichloride (anhydrous) hydrolysis of the present invention produces hydrochloric acid and destroys the dense oxidation film on aluminium powder surface, makes simple substance aluminium powder It is exposed；React since the aluminium powder activity exposed is higher with activating solvent the halogen atom that can be removed on activating solvent, With reaction make aluminium simple substance exposure it is more and more, make later with pvc response the chlorine atom in polyvinyl chloride with The removing of HCl form.HCl generates alchlor and H with reactive aluminum again2.Small molecule on carbochain end group is also with exothermic heat of reaction Gradually it is pyrolyzed.
Note: the alchlor in the present invention refers to aluminum trichloride (anhydrous).
Compared with prior art, the present invention having the following beneficial effects:
(1) present invention using aluminium powder as catalyst, using alchlor and iodine as initiator, can be lower than 100 DEG C under conditions of send out Raw efficient degradation, generates alchlor, alkene micro-molecular gas and polyacetylene, amorphous carbon, avoids existing most of halogen Plastics needs just can be carried out under the conditions of 800 DEG C of Pintsch process, and need nitrogen protection more, and product hydrochloric acid has very big corrosion The appearance of problem；It can be effectively reduced energy consumption, equipment avoided to corrode；
(2) present invention using aluminium powder as catalyst, put and aluminium powder be converted to aluminum trichloride (anhydrous) after answering, due to aluminium powder (mole Quality 27) about 1 ~ 1.3 ten thousand/ton of price, aluminum trichloride (anhydrous) (molal weight 133.3) 5,000/ton, one ton of aluminium powder is converted into The aluminum trichloride (anhydrous) of 5 tons of jin, the problem of halogen plastic degradation hardly possible is not only solved by this method, is more produced by degradative plastics Biggish economic value is given birth to.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art To obtain other drawings based on these drawings.
Fig. 1 a and 1b are respectively the thermogravimetric map of PVC, PVC and aluminium powder in the embodiment of the present invention 1.
Fig. 2 is the infrared spectrogram of purple liquid in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrogram of gained Halogen carbon compound after filter residue drying in the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of gained Halogen carbon compound after filter residue drying in the embodiment of the present invention 1.
Fig. 5 is the Raman spectrogram of gained Halogen carbon compound after filter residue drying in the embodiment of the present invention 1.
Fig. 6 is the thermogravimetric map of gained Halogen carbon compound and PVC after filter residue drying in the embodiment of the present invention 1.
Fig. 7 is the XRD spectra of Halogen carbon compound in the embodiment of the present invention 1.
Fig. 8 be in the embodiment of the present invention 1 yellow it is brilliant (Gu) infrared spectrogram of body.
Fig. 9 is the infrared spectrogram of gained Halogen carbon compound after filter residue drying in the embodiment of the present invention 2.
Figure 10 is the infrared spectrogram of gained Halogen carbon compound after filter residue drying in the embodiment of the present invention 1 and 3.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on this Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 58 DEG C, and (iodine is molten in aubergine for solution when reaction starts In carbon tetrachloride color), solution becomes atropurpureus and emerges simultaneously with a small amount of white cigarette after 10min；Start to emit in bottle after 12min small Bubble, bubble becomes larger more (reaction is acutely) when 14min and solution becomes ater；Reaction was completed after 31min, and solution is in thick；And Due to there is condensing unit, therefore the only relatively low gas of boiling point can be discharged；The gas being discharged in not logical hydrogen can make acid height Potassium manganate fades, and the gas being discharged after logical hydrogen can make silver nitrate generate white precipitate, pours into ethyl alcohol and releases big calorimetric in a flash Bottom of bottle has boiling phenomenon, and the yellow solid of a large amount of white cigarettes of emerging in bottle while bottle wall is dissolved to form yellow, viscous liquid cocurrent Enter bottom of bottle；When being filtered with sand core funnel, just start clearly to see yellow liquid in thick, filtered filter residue is in black Filter residue is put into glass culture dish and is put into 80 DEG C of baking oven and carries out drying 8h by color, and gained black solid is Halogen carbon compound； There is boiling phenomenon when filtrate is distilled, in bottle, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, By remaining liq pour into glass culture dish in drying box after 80 DEG C of drying 8h in yellow solid, brilliant (solid) body of the yellow is nothing Water alchlor.
By the thermogravimetric map of Fig. 1 a and 1b it can be seen that maximum peak after PVC and aluminium powder mixing in weightlessness in the first stage Value becomes larger.The factor of variation is caused mainly there are two aspects, first is that aluminium powder absorbs heat, temperature is up rushed, and needs higher temperature ability Find out pyrolysis；Second is that aluminium powder participates in exothermic heat of reaction, temperature is also toward rising.Weightless peak area becomes larger simultaneously, and fuel factor range becomes larger More illustrate that aluminium powder has participated in reaction.Since the presence of first stage aluminium realizes dechlorination, only remained in the weightlessness of second stage The bad therefore weightless peak-peak of carbon-carbon bond stability reduces.
When starting to bubble in bottle, the gas emerged is poured into the test tube for filling acid potassium permanganate with cuvette In, color is aubergine in original test tube, and aubergine, which is slowly taken off, when bubble is gradually emerged has ultimately become colourless, then during this Potassium permanganate is instilled constantly into test tube until not having bubble to emerge.This is because acid potassium permanganate has strong oxidizing property, energy Make potassium permanganate colour fading all has certain reproducibility, from experimentation it is seen that reacting the gaseous material generated, by It may determine that the gas boiling point being discharged in reaction system is very low in condenser pipe temperature is very low；It is extrapolated, is made according to reaction raw materials Potassium permanganate colour fading can only be organic matter, therefore the gas for emitting potassium permanganate colour fading of sening as an envoy to is alkene, i.e. ethylene (boiling point: -103.7 DEG C) or propylene (boiling point: -47.6 DEG C).Reaction equation:
5CH2=CH2+12KMnO4+18H2SO4==10CO2↑+12MnSO4+28H2O+6K2SO4
CH3CH=CH2+2KMnO4+3H2SO4==CH3COOH+CO2↑+2MnSO4+4H2O+K2SO4
When starting to bubble in bottle, the gas emerged is poured into the test tube for filling silver nitrate with cuvette, original test tube Interior colorless and transparent, bubble is gradually emerged, initially not variation, and being passed through after hydrogen has white solid generation in test tube, and several seconds Color becomes muddy milky in test tube afterwards.This is because having white precipitate generation in solution after pouring into after gas in test tube It is possible thereby to judge there is HCl small molecule in product.Reaction equation:
AgNO3+HCI→AgCl↓+HNO3
By the infrared spectrogram of Fig. 2 purple liquid it can be seen that wave-number range is in 4500 ~ 500cm-1, it is infrared to consult carbon tetrachloride In map it can be seen that only in 800 ~ 750cm-1There is the characteristic absorption peak of infrared spectroscopy at wave number, only exists in the following figure 791.33cm-1There is characteristic absorption peak, compares carbon tetrachloride infrared spectrum, can analyze out purple liquid, be mainly unreacted Carbon tetrachloride and a small amount of iodine.
As seen from Figure 3: wave-number range is in 4500 ~ 500cm-1, from polyvinyl chloride infared spectrum[16-18]In it can be seen that In 800 ~ 750cm-1There is the characteristic absorption peak of infrared spectroscopy at wave number, the absorption peak in the Main Analysis area, wave when analyzing infrared figure Number 794.60cm-1The absorption peak at place is mainly C-Cl stretching vibration absworption peak, the black solid product discovery after comparison reaction There is no absorption peaks can be seen that chlorine atom success is removed from polyvinyl chloride after reaction here；Simultaneously in-C=C- key In 1620 ~ 1680cm-1There is characteristic absorption peak at place, and as can be seen from the figure product is in 1646.48cm-1Place has characteristic absorption peak to say There is the presence of double bond in bright product.
As seen from Figure 4: black solid product grain is very big, and average grain diameter does not have agglomerated particle surface at 100 μm More coarse, shape is simultaneously irregular.
Using Raman spectrum[19]Black solid product after degradation is characterized, to obtain the change of its surface molecule structure The information of change.It is can be found that by the Raman spectrogram of Fig. 5 in 1549cm-1There is an acromion at place, and polyacetylene Raman spectrogram[21] In 1530cm-1There is spike in left and right, it is possible thereby to which inferring has the presence of polyacetylene in black solid product.
Carbon tetrachloride solid will be removed and do thermogravimetric, can be seen that solid is mixture in Fig. 6, since heating rate is very fast, from 25 DEG C of beginnings are weightless, are 200 DEG C in temperature and appear below first weightless platform, and weight loss is close to 30wt.% at this time.This What part lost is the small-molecule substances such as ethylene or propylene and part aluminum trichloride (anhydrous), increases lasting lose with temperature later Weight, weight loss is 60wt.% or more, predominantly aluminum trichloride (anhydrous) at this time.Final remaining residue is 44.3wt.%.
PVC is degraded in carbon tetrachloride solvent in the Halogen carbon compound of generation and the thermogravimetric map of PVC in comparison diagram 6 Two lines obviously can be seen that pyrolysis has changed a lot, after the addition of solvent obviously it can be seen that PVC pyrolysis temperature It being greatly lowered, it is seen that largely effective feasible when this method, Cong Tuzhong judges to generate many small-molecule substances, The initial temperature and peak value being thus pyrolyzed in the first stage all reduce very much；Second stage after pyrolysis in the first stage simultaneously Since halogen is all stripped of in the first stage, only surplus carbon-carbon bond stability is not so good therefore weightlessness peak value reduces；And PVC is pyrolyzed Residue afterwards is compared for the product generated after 9.2wt.%, with degradation it can be found that the moieties after degradation are pyrolyzed reduced performance More stable, the XRD spectra analysis in conjunction with Fig. 7 is it can be concluded that contain part amorphous carbon in the product after PVC degradation.
By PVC in Fig. 7 degrade in carbon tetrachloride solvent the Halogen carbon compound of generation XRD spectrum it can be seen that Occur first strong diffraction maximum at 10.38 °, in 26.86 ° of appearance, second strong diffraction maximum, passes through comparison graphite and graphite The XRD spectrum of alkene, since graphene is obtained by hydrazine hydrate reduction, the peak near 10 ° is completely disappeared, and the characteristic peak of graphite exists Near 10 °, second strong diffraction maximum is the characteristic peak of graphite.So product has the feature of graphite but is not that graphene can be with Judge the structure for having amorphous carbon in product.
As Fig. 8 yellow it is brilliant (Gu) shown in the infrared spectrogram of body: its wave-number range is in 4500 ~ 500cm-1, in 637.56cm-1There is strong absworption peak at place, and consulting literatures are found in 601cm-1There is Al-Cl stretching vibration absworption peak at place, due to alchlor have it is multiple Al-Cl stretching vibration absworption peak therefore wave number are to mobile at long wave number, it can judge there is alchlor in yellow solid.
Embodiment 2
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.025g alchlor, 0.025g iodine, 10g bromoethane is put into the three-necked flask containing magneton, is reacted under the conditions of 58 DEG C, and solution is in orange when reaction starts, and is had Steam bubble is emerged, and is disappeared after 30s；PVC has Swelling in bottle after 19min, and solid is formed on surface, and color is brown；Bottle after 25min Interior reactant becomes ater；Reaction was completed by 41min, and the gas being discharged in not logical hydrogen can make acid potassium permanganate fade； The gas being discharged after logical hydrogen cannot make silver nitrate generate white precipitate；As the carry out three-necked flask bottle wall of distillation has yellow solid Body, and have a large amount of white cigarettes in bottle, there is fraction outflow at 37 DEG C, color is in aubergine；Filter residue is in black, and it is solid to pour into ethanol washing Body when being filtered with sand core funnel, can see that black purple liquid flows down；There is boiling phenomenon when filtrate is distilled, in bottle, and at 78 DEG C There is a fraction outflow, darkly purple is thick when there is not much left for solution；Darkly violet solid after drying.
It is led afterwards in active solvent (carbon tetrachloride in embodiment 1 being replaced with bromoethane, other response parameters are constant) It to change in the reacting phenomenon of first stage of reaction, Swelling occurs under bromoethane activator in PVC, and color is also sent out Variation is given birth to, but there is no variations by the characterization discovery product of gas, solid product.
By the infrared spectrum of Fig. 9 it can be seen that wave-number range is in 4500 ~ 500cm-1, can from polyvinyl chloride infared spectrum To find out in 800 ~ 750cm-1There is the characteristic absorption peak of infrared spectroscopy at wave number, the absorption in Main Analysis area when analyzing infrared figure Peak；Wave number 794cm-1The absorption peak at place is mainly C-Cl stretching vibration absworption peak, and the black product discovery after comparison reaction exists There is no absorption peaks can be seen that chlorine atom success is removed from polyvinyl chloride after reaction herein.
Embodiment 3
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.035g alchlor, 0.035g iodine, 7g Bromoethane and 3g carbon tetrachloride are put into the three-necked flask containing magneton, are reacted under the conditions of 58 DEG C, and solution is in when reaction starts Purple powder color；Start bubbling after 7min in bottle and darkens；Color becomes ater simultaneously with a small amount of white cigarette after 16min. 48min reaction terminates.And due to there is condensing unit, therefore the only relatively low gas of boiling point can be discharged.It is discharged in not logical hydrogen Gas acid potassium permanganate can be made to fade.The gas being discharged after logical hydrogen can make silver nitrate generate white precipitate.With distillation Carry out three-necked flask bottle wall have yellow solid, and have a large amount of white cigarettes in bottle, have fraction outflow at 70 DEG C, color is in purplish red Color.Filter residue is in ater.Ethanol washing solid is poured into, when being filtered with sand core funnel, can see that yellow liquid flows down.Filtrate is steamed When evaporating, there is boiling phenomenon in bottle, and there are fraction outflow in 78 DEG C of whens.When having crystal precipitation in solution, liquid is poured out, in Huang after drying Color solid.
By Figure 10 with carbon tetrachloride and bromoethane hybrid activator and carbon tetrachloride infrared spectrum it can be seen that wave number model It is trapped among 4500 ~ 500cm-1, the solid product of the degradation of the two PVC is in 794cm-1Place does not have C-Cl stretching vibration absworption peak, can It is removed with finding out chlorine element also to succeed from PVC.
Embodiment 4
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 0.5g aluminium powder, 0.06g alchlor, 0.06g iodine, 6g tetra- Chlorination carbon is put into the three-necked flask containing magneton, is reacted under the conditions of 45 DEG C, and solution is in aubergine (iodine dissolution when reaction starts Color in carbon tetrachloride), solution becomes atropurpureus and emerges simultaneously with a small amount of white cigarette after 11min；Start in bottle after 23min Emit vesicle, bubble becomes larger more (reaction is acutely) when 30min and solution becomes ater；Reaction was completed after 40min, and solution is in sticky Shape；And due to there is condensing unit, therefore the only relatively low gas of boiling point can be discharged；The gas being discharged in not logical hydrogen can make acid Property potassium permanganate fade, the gas being discharged after logical hydrogen can make silver nitrate generate white precipitate, pour into ethyl alcohol and release in a flash greatly Calorimetric bottom of bottle has boiling phenomenon, and the yellow solid of a large amount of white cigarettes of emerging in bottle while bottle wall is dissolved to form yellow, viscous liquid And flow into bottom of bottle；When being filtered with sand core funnel, just start clearly to see yellow liquid in thick, filtered filter residue is in Filter residue is put into glass culture dish and is put into 80 DEG C of baking oven and carries out drying 8h by ater, and gained black solid is Halogen containing carbonization Close object；There is boiling phenomenon when filtrate is distilled, in bottle, and there are fraction outflow, stopping when having yellow crystals precipitation in solution in 78 DEG C of whens Distillation, by remaining liq pour into glass culture dish in drying box after 80 DEG C of drying 8h in yellow solid, the yellow crystalline substance (Gu) Body is aluminum trichloride (anhydrous).
Embodiment 5
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.5g aluminium powder, 0.08g alchlor, 0.08g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 50 DEG C, and solution is in aubergine when reaction starts, Solution becomes atropurpureus while emerging with a small amount of white cigarette after 12min；Start to emit vesicle after 20min in bottle, bubble becomes larger when 30min Become more (reaction is violent) and solution becomes ater；Reaction was completed after 45min, and solution is in thick；And due to there is condensing unit, Therefore the only relatively low gas of boiling point can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, and lead to hydrogen The gas being discharged after gas can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has boiling phenomenon, The yellow solid of a large amount of white cigarettes of emerging in bottle while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is leaked with sand core When bucket filters, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass It is put into 80 DEG C of baking oven in glass culture dish and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, in bottle There is a boiling phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass Glass culture dish is in yellow solid after 80 DEG C of drying 8h in drying box, and brilliant (solid) body of the yellow is aluminum trichloride (anhydrous).
Embodiment 6
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 65 DEG C, and solution is in aubergine, 8min when reaction starts Solution becomes atropurpureus while emerging with a small amount of white cigarette afterwards；Start to emit vesicle after 12min in bottle, bubble becomes larger more when 15min (reaction is violent) and solution becomes ater；Reaction was completed after 50min, and solution is in thick；And due to there is condensing unit, therefore only The gas for having boiling point relatively low can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, after leading to hydrogen The gas of discharge can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has a boiling phenomenon, in bottle The yellow solid of a large amount of white cigarettes of emerging while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is taken out with sand core funnel When filter, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass training It is put into 80 DEG C of baking oven in feeding ware and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, there is boiling in bottle Rise phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass training Supporting ware is in yellow solid after 80 DEG C of drying 8h in drying box, the yellow it is brilliant (Gu) body is aluminum trichloride (anhydrous).
Embodiment 7
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 70 DEG C, and solution is in aubergine, 8min when reaction starts Solution becomes atropurpureus while emerging with a small amount of white cigarette afterwards；Start to emit vesicle after 10min in bottle, bubble becomes larger more when 22min (reaction is violent) and solution becomes ater；Reaction was completed after 50min, and solution is in thick；And due to there is condensing unit, therefore only The gas for having boiling point relatively low can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, after leading to hydrogen The gas of discharge can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has a boiling phenomenon, in bottle The yellow solid of a large amount of white cigarettes of emerging while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is taken out with sand core funnel When filter, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass training It is put into 80 DEG C of baking oven in feeding ware and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, there is boiling in bottle Rise phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass training Supporting ware is in yellow solid after 80 DEG C of drying 8h in drying box, the yellow it is brilliant (Gu) body is aluminum trichloride (anhydrous).
Embodiment 8
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 75 DEG C, and solution is in aubergine, 6min when reaction starts Solution becomes atropurpureus while emerging with a small amount of white cigarette afterwards；Start to emit vesicle after 12min in bottle, bubble becomes larger more when 23min (reaction is violent) and solution becomes ater；Reaction was completed after 30min, and solution is in thick；And due to there is condensing unit, therefore only The gas for having boiling point relatively low can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, after leading to hydrogen The gas of discharge can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has a boiling phenomenon, in bottle The yellow solid of a large amount of white cigarettes of emerging while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is taken out with sand core funnel When filter, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass training It is put into 80 DEG C of baking oven in feeding ware and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, there is boiling in bottle Rise phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass training Supporting ware is in yellow solid after 80 DEG C of drying 8h in drying box, the yellow it is brilliant (Gu) body is aluminum trichloride (anhydrous).
Embodiment 9
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 100 DEG C, and solution is in aubergine when reaction starts, Solution becomes atropurpureus while emerging with a small amount of white cigarette after 6min；Start to emit vesicle after 10min in bottle, bubble becomes larger when 25min Become more (reaction is violent) and solution becomes ater；Reaction was completed after 32min, and solution is in thick；And due to there is condensing unit, Therefore the only relatively low gas of boiling point can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, and lead to hydrogen The gas being discharged after gas can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has boiling phenomenon, The yellow solid of a large amount of white cigarettes of emerging in bottle while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is leaked with sand core When bucket filters, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass It is put into 80 DEG C of baking oven in glass culture dish and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, in bottle There is a boiling phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass Glass culture dish is in yellow solid after 80 DEG C of drying 8h in drying box, and brilliant (solid) body of the yellow is aluminum trichloride (anhydrous).
Embodiment 10
A kind of Thermal degradation method of halogen plastics, by 1.5g PVC, 1.0g aluminium powder, 0.05g alchlor, 0.05g iodine, 10g Carbon tetrachloride is put into the three-necked flask containing magneton, is reacted under the conditions of 43 DEG C, and solution is in aubergine when reaction starts. Solution becomes atropurpureus while emerging with a small amount of white cigarette after 14min；Start to emit vesicle after 20min in bottle, bubble becomes larger when 31min Become more (reaction is violent) and solution becomes ater；Reaction was completed after 40min, and solution is in thick；And due to there is condensing unit, Therefore the only relatively low gas of boiling point can be discharged；The gas being discharged in not logical hydrogen can make acid potassium permanganate fade, and lead to hydrogen The gas being discharged after gas can make silver nitrate generate white precipitate, and pouring into ethyl alcohol and releasing big calorimetric bottom of bottle in a flash has boiling phenomenon, The yellow solid of a large amount of white cigarettes of emerging in bottle while bottle wall is dissolved to form yellow, viscous liquid and flow into bottom of bottle；It is leaked with sand core When bucket filters, just start clearly to see yellow liquid in thick, filtered filter residue is in ater, and filter residue is put into glass It is put into 80 DEG C of baking oven in glass culture dish and carries out drying 8h, gained black solid is Halogen carbon compound；When filtrate is distilled, in bottle There is a boiling phenomenon, and there are fraction outflow in 78 DEG C of whens, stop distillation when having yellow crystals precipitation in solution, remaining liq is poured into glass Glass culture dish is in yellow solid after 80 DEG C of drying 8h in drying box, and brilliant (solid) body of the yellow is aluminum trichloride (anhydrous).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of Thermal degradation method of halogen plastics, it is characterised in that: using PVC as raw material, using aluminium powder as catalyst, with trichlorine Changing aluminium and iodine is initiator, and in activating solvent system, reaction generates alchlor under the conditions of 43 ~ 100 DEG C and Halogen is carbon containing Compound.
2. the Thermal degradation method of halogen plastics as described in claim 1, it is characterised in that: reaction condition is 45 ~ 75 DEG C.
3. the Thermal degradation method of halogen plastics as claimed in claim 2, it is characterised in that: reaction condition is 58 DEG C.
4. the Thermal degradation method of halogen plastics as described in claim 1, it is characterised in that: the activating solvent is bromoethane And/or carbon tetrachloride.
5. the Thermal degradation method of halogen plastics as claimed in claim 4, it is characterised in that: the activating solvent is four chlorinations Carbon.
6. the Thermal degradation method of halogen plastics as claimed in claim 4, it is characterised in that: the matter of the PVC and activating solvent Measure 1.5 ~ 15:1 of ratio.
7. the Thermal degradation method of halogen plastics as described in claim 1, it is characterised in that: contain in the Halogen carbon compound There are polyacetylene and amorphous carbon.
8. such as the Thermal degradation method of any halogen plastics in claim 1 ~ 7, it is characterised in that: the PVC and aluminium powder Mass ratio be 1 ~ 3:1.
9. the Thermal degradation method of halogen plastics as claimed in claim 8, it is characterised in that: the mass ratio of the PVC and aluminium powder For 3:2.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608136A (en) * 1991-12-20 1997-03-04 Kabushiki Kaisha Toshiba Method and apparatus for pyrolytically decomposing waste plastic
JP2002020534A (en) * 2000-07-07 2002-01-23 Tsukishima Kikai Co Ltd Method for thermally decomposing chlorine-containing plastic waste material
JP2006110531A (en) * 2004-10-13 2006-04-27 Aasu Recycle Kk Process for separating valuable materials from mixed plastics containing pvc(polyvinylidene chloride as well) and pet, and plastics/aluminum composite films
CN106349500A (en) * 2016-09-23 2017-01-25 苏州大学 Dechlorination method for chlorine-containing plastic
WO2018011642A1 (en) * 2016-07-13 2018-01-18 Sabic Global Technologies, B.V. A process which does simultaneous dehydrochlorination and hydrocracking of pyrolysis oils from mixed plastic pyrolysis while achieving selective hydrodealkylation of c9+ aromatics

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608136A (en) * 1991-12-20 1997-03-04 Kabushiki Kaisha Toshiba Method and apparatus for pyrolytically decomposing waste plastic
JP2002020534A (en) * 2000-07-07 2002-01-23 Tsukishima Kikai Co Ltd Method for thermally decomposing chlorine-containing plastic waste material
JP2006110531A (en) * 2004-10-13 2006-04-27 Aasu Recycle Kk Process for separating valuable materials from mixed plastics containing pvc(polyvinylidene chloride as well) and pet, and plastics/aluminum composite films
WO2018011642A1 (en) * 2016-07-13 2018-01-18 Sabic Global Technologies, B.V. A process which does simultaneous dehydrochlorination and hydrocracking of pyrolysis oils from mixed plastic pyrolysis while achieving selective hydrodealkylation of c9+ aromatics
CN106349500A (en) * 2016-09-23 2017-01-25 苏州大学 Dechlorination method for chlorine-containing plastic

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