CN103159978A - Processing method of flame retardant plastic containing halide and antimony oxide - Google Patents
Processing method of flame retardant plastic containing halide and antimony oxide Download PDFInfo
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- CN103159978A CN103159978A CN2011104148216A CN201110414821A CN103159978A CN 103159978 A CN103159978 A CN 103159978A CN 2011104148216 A CN2011104148216 A CN 2011104148216A CN 201110414821 A CN201110414821 A CN 201110414821A CN 103159978 A CN103159978 A CN 103159978A
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- flame retardant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The present invention provides a processing method of flame retardant plastic containing halide and antimony oxide, comprising washing, crushing, adding sulfuric acid for leaching to obtain an acid leaching mixed product, recycling plastic, recycling antimony and recycling halogen acid. The method can change waste into treasure and comprehensively recycle the antimony, halogen and plastic in the flame retardant plastic, is simple in process and has no pollution, and has enormous social and economic benefits.
Description
Technical field
The present invention relates to the processing of industrial waste, relate in particular to the treatment process of the flame retardant plastics of a kind of halide and sb oxide.
Background technology
Halogen-Sb system fire retardant that halogenide (chlorine system and bromine are) and sb oxide (being mainly antimonous oxide) are combined to form, additive flame retardant as a kind of traditional technical maturity, because of its flame retardant effect obvious and cheap by large-scale application to flame retardant of plastic, particularly electric upper thermoplastics is fire-retardant.
Along with the halide of early application and the flame retardant plastics of sb oxide have reached work-ing life, and this flame retardant plastics is about to arrive work-ing life on a large scale, and more and more this flame retardant plastics is eliminated becomes industrial waste.Therefore, processing again of these flame retardant plastics day by day becomes a problem that merits attention.
At present, the treatment process for these flame retardant plastics mainly contains: recycle after landfill, burning and direct modification etc.Yet these methods have respectively following defective: (1) metallic antimony is resource rare on the earth, and it is expensive, and directly landfill will cause the serious waste of antimony resource; (2) halogenide amount of being fuming in burning process is large and discharge a large amount of poisonous and mordant gases, and environment is caused serious pollution; And (3) are direct with in the method that recycles after the flame retardant plastics modification, and the existence of fire retardant causes certain influence to modifying plastics.
Summary of the invention
For addressing the above problem, the present invention aims to provide the treatment process of the flame retardant plastics of a kind of halide and sb oxide.The method can turn waste into wealth, and comprehensively reclaims antimony, halogen and plastics in described flame retardant plastics, and technique is simple and pollution-free, has huge Social benefit and economic benefit.
The invention provides the treatment process of the flame retardant plastics of a kind of halide and sb oxide, comprise the following steps:
(1) clean fragmentation: get the flame retardant plastics of halide and sb oxide, clean, fragmentation makes the flame retardant plastics particle;
(2) acid-leaching reaction: get flame retardant plastics particle described in step (1), add sulphuric acid soln to carry out acidleach, the acidleach temperature is 280～350 ℃, the acid-leaching reaction time is 3～4 hours, make the acidleach mix products, in the time of acid-leaching reaction, haloid acid is reclaimed in condensation, makes the mixing solutions that contains haloid acid;
(3) recycled plastic: get acidleach mix products described in step (2), standing 5～10 minutes, after layering, liquid level is discharged, collect plastic layer and namely get recycled plastic;
(4) reclaim antimony: get liquid level described in step (3), add alkali, go back to adjust pH to 1.0～2.0, add iron replacement, the filtering separation solid-liquid is got filter residue and is namely got the needle antimony powder;
(5) reclaim haloid acid: get the mixing solutions that contains haloid acid described in step (2), add hydrogen peroxide solution oxybromination hydrogen, then with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions.
In step (1), the halide that the present invention adopts and the flame retardant plastics of sb oxide can derive from waste and old electric electrical equipment and waste and old building materials etc., wherein contain the halogen-Sb system fire retardant that is combined to form by halogenide and sb oxide.Preferably, the particle diameter of flame retardant plastics particle is 10～100 μ m.
In step (2), get flame retardant plastics particle described in step (1), add sulphuric acid soln to carry out acidleach, stir simultaneously, make the flame retardant plastics particle softening.The acidleach temperature is 280～350 ℃, acid-leaching reaction 3～4 hours, and the inorganics in the flame retardant plastics particle is leached fully, makes the acidleach mix products, and described inorganics comprises sb oxide, molybdate, zinc borate and oxyhydroxide etc.In the acidleach process, the halogenide in flame retardant plastics forms haloid acid.Reclaim the haloid acid of volatilization by condensate recycling device, make the mixing solutions that contains haloid acid.Preferably, the concentration of sulphuric acid soln is 60～98%.Preferably, in sulfuric acid and flame retardant plastics particle, the ratio of the mole number of contained antimony is 1: 0.05～0.2.Preferably, condensing temperature is 220～280 ℃.Preferably, the mixing solutions that contains haloid acid further is cleaned.Be specially by refining plant (absorption unit of acetone for example is housed) and remove a small amount of water-fast organism.
In step (3), get acidleach mix products described in step (2), made plastics and mixing solutions layering after softening in standing 5～10 minutes.Inorganics is dissolved in sulfuric acid and forms mixing solutions and be liquid level.This liquid level is discharged, collect plastic layer and namely get recycled plastic.Can re-use after the recycled plastic modification.
In step (4), get liquid level described in step (3), this liquid level is the sulphuric acid soln that contains metal ion, contains antimony ion and a small amount of zine ion, molybdenum ion, aluminum ion and magnesium ion.Add alkali, go back to adjust pH to 1.0～2.0.Add subsequently iron replacement.The filtering separation solid-liquid is got filter residue and is namely got the needle antimony powder.Preferably, metallic iron is 1: 0.2～0.9 with the ratio of the mole number of antimony.
In step (5), get the mixing solutions that contains haloid acid described in step (2), add hydrogen peroxide solution oxybromination hydrogen, then with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions.Preferably, the massfraction of hydrogen peroxide is 15～30%, and the ratio 1: 0.6～0.8 of described hydrogen peroxide and the mole number of hydrogen bromide was 30～50 ℃ of reactions 10～30 minutes.
The treatment process of the flame retardant plastics of a kind of halide provided by the invention and sb oxide, has following beneficial effect: can turn waste into wealth, comprehensive antimony, halogen and the plastics that reclaim in described flame retardant plastics, technique is simple and pollution-free, has huge Social benefit and economic benefit.
Description of drawings
Fig. 1 is the schematic flow sheet of the embodiment of the present invention.
Embodiment
The following stated is the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.Fig. 1 is the schematic flow sheet of the embodiment of the present invention.
Embodiment one
The treatment process of the flame retardant plastics of a kind of halide and sb oxide comprises the following steps:
(1) clean fragmentation
Get the flame retardant plastics of halide and sb oxide, clean, fragmentation, making particle diameter is the flame retardant plastics particle of 10～100 μ m;
(2) acid-leaching reaction
Get flame retardant plastics particle described in step (1), adding concentration is that 60% sulphuric acid soln carries out acidleach, in sulfuric acid and flame retardant plastics particle, the ratio of the mole number of contained antimony is 1: 0.05, the acidleach temperature is 280 ℃, the acid-leaching reaction time is 4 hours, makes the acidleach mix products, and in the time of acid-leaching reaction, haloid acid is reclaimed in condensation, condensing temperature is 220～240 ℃, makes the mixing solutions that contains haloid acid;
(3) recycled plastic: get acidleach mix products described in step (2), standing 5 minutes, after layering, liquid level is discharged, collect plastic layer and namely get recycled plastic;
(4) reclaim antimony: get liquid level described in step (3), add alkali, return adjust pH to 1.0, add iron replacement, metallic iron is 1: 0.2 with the ratio of the mole number of antimony, and the filtering separation solid-liquid is got filter residue and namely got the needle antimony powder;
(5) reclaim haloid acid: get the mixing solutions that contains haloid acid described in step (2), adding massfraction is 15% hydrogen peroxide, the ratio of described hydrogen peroxide and the mole number of hydrogen bromide 1: 0.6,30 ℃ of reactions 30 minutes, with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions again.
Embodiment two
The treatment process of the flame retardant plastics of a kind of halide and sb oxide comprises the following steps:
(1) clean fragmentation: get the flame retardant plastics of halide and sb oxide, clean, fragmentation, making particle diameter is the flame retardant plastics particle of 10～100 μ m;
(2) acid-leaching reaction: get flame retardant plastics particle described in step (1), adding concentration is that 98% sulphuric acid soln carries out acidleach, in sulfuric acid and flame retardant plastics particle, the ratio of the mole number of contained antimony is 1: 0.2, the acidleach temperature is 350 ℃, the acid-leaching reaction time is 3 hours, makes the acidleach mix products, and in the time of acid-leaching reaction, haloid acid is reclaimed in condensation, condensing temperature is 260～280 ℃, makes the mixing solutions that contains haloid acid;
(3) recycled plastic: get acidleach mix products described in step (2), standing 10 minutes, after layering, liquid level is discharged, collect plastic layer and namely get recycled plastic;
(4) reclaim antimony: get liquid level described in step (3), add alkali, return adjust pH to 2.0, add iron replacement, metallic iron is 1: 0.9 with the ratio of the mole number of antimony, and the filtering separation solid-liquid is got filter residue and namely got the needle antimony powder;
(5) reclaim haloid acid: get the mixing solutions that contains haloid acid described in step (2), adding massfraction is 30% hydrogen peroxide, the ratio of described hydrogen peroxide and the mole number of hydrogen bromide 1: 0.8,50 ℃ of reactions 10 minutes, with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions again.
Embodiment three
The treatment process of the flame retardant plastics of a kind of halide and sb oxide comprises the following steps:
(1) clean fragmentation: get the flame retardant plastics of halide and sb oxide, clean, fragmentation, making particle diameter is the flame retardant plastics particle of 10～100 μ m;
(2) acid-leaching reaction: get flame retardant plastics particle described in step (1), adding concentration is that 80% sulphuric acid soln carries out acidleach, in sulfuric acid and flame retardant plastics particle, the ratio of the mole number of contained antimony is 1: 0.1, the acidleach temperature is 320 ℃, the acid-leaching reaction time is 3 hours, make the acidleach mix products, in the time of acid-leaching reaction, haloid acid is reclaimed in condensation, condensing temperature is 250～260 ℃, make the mixing solutions that contains haloid acid, the mixing solutions that contains haloid acid is further removed a small amount of water-fast organism by the absorption unit that acetone is housed;
(3) recycled plastic: get acidleach mix products described in step (2), standing 10 minutes, after layering, liquid level is discharged, collect plastic layer and namely get recycled plastic;
(4) reclaim antimony: get liquid level described in step (3), add alkali, return adjust pH to 1.5, add iron replacement, metallic iron is 1: 0.5 with the ratio of the mole number of antimony, and the filtering separation solid-liquid is got filter residue and namely got the needle antimony powder;
(5) reclaim haloid acid: get the mixing solutions that contains haloid acid described in step (2), adding massfraction is 25% hydrogen peroxide, the ratio of described hydrogen peroxide and the mole number of hydrogen bromide 1: 0.7,40 ℃ of reactions 20 minutes, with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions again.
Claims (8)
1. the treatment process of the flame retardant plastics of a halide and sb oxide, is characterized in that, comprises the following steps:
(1) clean fragmentation: get the flame retardant plastics of halide and sb oxide, clean, fragmentation makes the flame retardant plastics particle;
(2) acid-leaching reaction: get flame retardant plastics particle described in step (1), add sulphuric acid soln to carry out acidleach, the acidleach temperature is 280～350 ℃, the acid-leaching reaction time is 3～4 hours, make the acidleach mix products, in the time of acid-leaching reaction, haloid acid is reclaimed in condensation, makes the mixing solutions that contains haloid acid;
(3) recycled plastic: get acidleach mix products described in step (2), standing 5～10 minutes, after layering, liquid level is discharged, collect plastic layer and namely get recycled plastic;
(4) reclaim antimony: get liquid level described in step (3), add alkali, go back to adjust pH to 1.0～2.0, add iron replacement, the filtering separation solid-liquid is got filter residue and is namely got the needle antimony powder;
(5) reclaim haloid acid: get the mixing solutions that contains haloid acid described in step (2), add hydrogen peroxide solution oxybromination hydrogen, then with carbon tetrachloride extraction bromine wherein, reclaim respectively hydrochloric acid soln and bromine solutions.
2. the method for claim 1, is characterized in that, in described step (1), the particle diameter of flame retardant plastics particle is 10～100 μ m.
3. the method for claim 1, is characterized in that, in described step (2), the concentration of sulphuric acid soln is 60～98%.
4. the method for claim 1, is characterized in that, in described step (2) in sulfuric acid and flame retardant plastics particle the ratio of the mole number of contained antimony be 1: 0.05～0.2.
5. the method for claim 1, is characterized in that, in described step (2), condensing temperature is 220～280 ℃.
6. the method for claim 1, is characterized in that, the mixing solutions that contains haloid acid in described step (2) further is cleaned.
7. the method for claim 1, is characterized in that, in described step (4), iron is 1: 0.2～0.9 with the ratio of the mole number of antimony.
8. the method for claim 1, is characterized in that, the massfraction of hydrogen peroxide is 15～30% in described step (5), and the ratio 1: 0.6～0.8 of described hydrogen peroxide and the mole number of hydrogen bromide was 30～50 ℃ of reactions 10～30 minutes.
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| CN201110414821.6A CN103159978B (en) | 2011-12-13 | 2011-12-13 | Processing method of flame retardant plastic containing halide and antimony oxide |
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| CN201110414821.6A CN103159978B (en) | 2011-12-13 | 2011-12-13 | Processing method of flame retardant plastic containing halide and antimony oxide |
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| CN103159978A true CN103159978A (en) | 2013-06-19 |
| CN103159978B CN103159978B (en) | 2015-05-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321848A (en) * | 2020-07-31 | 2021-08-31 | 上海交通大学 | Method for synchronously removing antimony and bromine from electronic waste flame-retardant plastic and recycling plastic matrix |
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| JP2002179833A (en) * | 2000-12-12 | 2002-06-26 | Asahi Kasei Corp | Method for separating recovered flame retardant components |
| CN1358213A (en) * | 2000-04-27 | 2002-07-10 | 旭化成株式会社 | Method for treaitng resin composition |
| JP2002194136A (en) * | 2000-12-26 | 2002-07-10 | Asahi Kasei Corp | Method for recovering styrenic resin |
| CN101509080A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Method for comprehensively processing stibium smelt arsenic alkaline residue and producing colloid antimony peroxide |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358213A (en) * | 2000-04-27 | 2002-07-10 | 旭化成株式会社 | Method for treaitng resin composition |
| JP2002179833A (en) * | 2000-12-12 | 2002-06-26 | Asahi Kasei Corp | Method for separating recovered flame retardant components |
| JP2002194136A (en) * | 2000-12-26 | 2002-07-10 | Asahi Kasei Corp | Method for recovering styrenic resin |
| CN101509080A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Method for comprehensively processing stibium smelt arsenic alkaline residue and producing colloid antimony peroxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321848A (en) * | 2020-07-31 | 2021-08-31 | 上海交通大学 | Method for synchronously removing antimony and bromine from electronic waste flame-retardant plastic and recycling plastic matrix |
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