CN104511369B - Method for waste mixed plastic separation - Google Patents
Method for waste mixed plastic separation Download PDFInfo
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- CN104511369B CN104511369B CN201510027566.8A CN201510027566A CN104511369B CN 104511369 B CN104511369 B CN 104511369B CN 201510027566 A CN201510027566 A CN 201510027566A CN 104511369 B CN104511369 B CN 104511369B
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- 239000004033 plastic Substances 0.000 title claims abstract description 157
- 229920003023 plastic Polymers 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000926 separation method Methods 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 56
- 238000005188 flotation Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000007667 floating Methods 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 32
- 239000008399 tap water Substances 0.000 claims description 21
- 235000020679 tap water Nutrition 0.000 claims description 21
- 239000008396 flotation agent Substances 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 13
- 239000013535 sea water Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 241000287127 Passeridae Species 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000004793 Polystyrene Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012994 photoredox catalyst Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- 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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- Engineering & Computer Science (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种废旧混合塑料的分离方法,属于废旧塑料回收技术领域。The invention relates to a method for separating waste and old mixed plastics, belonging to the technical field of waste and old plastics recycling.
背景技术Background technique
塑料工业的迅速发展、塑料的大量消费以及塑料较短的使用周期使得塑料废弃物的数量急剧增加。废旧塑料的处理方式为焚烧和填埋,产生了严重的环境污染和资源的浪费。因此,对废旧塑料的回收利用已得到高度重视。对废旧塑料回收过程,需要对不同的塑料进行分离,目前塑料的分离是制约废旧塑料回收过程的瓶颈环节。开发的混合塑料分离技术包括手工分拣、重力分离、浮选、静电分离和选择性溶解等方法。塑料的手工分拣过程劳动强度大、工作环境恶劣、分离效率低。重力分离和静电分离对物理性质相近的混合塑料的分离有很大局限性。选择性溶剂成本高,并且有机溶剂具有很大毒性。此外,塑料回收利润低以及废旧塑料的多样性也限制了塑料分离技术的开发。因此,开发低成本、适应性强、分离效率高的分离技术是本领域的重要问题。The rapid development of the plastics industry, the massive consumption of plastics, and the short life cycle of plastics have led to a sharp increase in the amount of plastic waste. The disposal methods of waste plastics are incineration and landfill, resulting in serious environmental pollution and waste of resources. Therefore, the recycling of waste plastics has been highly valued. For the recycling process of waste plastics, it is necessary to separate different plastics. At present, the separation of plastics is the bottleneck link restricting the recycling process of waste plastics. The mixed plastics separation technologies developed include methods such as manual sorting, gravity separation, flotation, electrostatic separation and selective dissolution. The manual sorting process of plastics is labor-intensive, the working environment is harsh, and the separation efficiency is low. Gravity separation and electrostatic separation have great limitations on the separation of mixed plastics with similar physical properties. Selective solvents are costly and organic solvents are very toxic. In addition, the low profit of plastic recycling and the diversity of waste plastics also limit the development of plastic separation technology. Therefore, it is an important issue in this field to develop a separation technology with low cost, strong adaptability and high separation efficiency.
发明内容Contents of the invention
针对现有技术中对废旧混合塑料进行分离的方法存在的缺陷,本发明的目的是在于提供一种以浮沉分离和浮选方法相结合对废旧塑料中的多种塑料成分进行高效选择性分离的方法,该方法操作简单、成本低,满足工业化应用生产。Aiming at the defects existing in the methods for separating waste mixed plastics in the prior art, the purpose of the present invention is to provide a method for efficiently and selectively separating various plastic components in waste plastics by combining floating-sink separation and flotation methods. The method has the advantages of simple operation and low cost, and satisfies industrial application and production.
本发明提供了一种废旧混合塑料分离的方法,所述的废旧混合塑料中包含至少一种密度相对较小的轻组分塑料和至少两种密度相近且密度相对较大的重组分塑料,其中,重组分塑料中至少含有一种含极性基团的塑料和不含极性基团的塑料;将废旧混合塑料破碎成混合塑料颗粒,所得混合塑料颗粒加入到液体介质I中进行沉浮分离,沉浮分离得到密度小于液体介质I的轻组分塑料颗粒和密度大于液体介质I的塑料颗粒,所得重组分塑料颗粒加入到液体介质II中在70~100℃温度下进行表面处理,经表面处理后的重组分塑料颗粒通过浮选剂进行浮选分离,分离得到含极性基团的塑料颗粒和不含极性基团的塑料颗粒。The invention provides a method for separating waste and old mixed plastics. The waste and old mixed plastics contain at least one light component plastic with relatively low density and at least two heavy component plastics with similar density and relatively high density, wherein , the heavy component plastic contains at least one kind of plastic containing polar groups and plastics without polar groups; the waste mixed plastics are broken into mixed plastic particles, and the obtained mixed plastic particles are added to liquid medium I for sinking and floating separation, Light component plastic particles with a density lower than liquid medium I and plastic particles with a density greater than liquid medium I are obtained by sinking and floating separation, and the obtained heavy component plastic particles are added to liquid medium II for surface treatment at a temperature of 70-100°C. After surface treatment The heavy component plastic particles are separated by flotation by flotation agent, and the plastic particles containing polar groups and the plastic particles without polar groups are separated.
本发明的对废旧混合塑料分离的方法还包括以下优选方案:The method for separating waste and old mixed plastics of the present invention also includes the following preferred solutions:
优选的方案中液体介质I密度在970~1200kg/m3之间,根据待分离的废旧混合塑料颗粒的密度选择合适密度的液体介质I。In the preferred solution, the density of the liquid medium I is between 970 and 1200 kg/m 3 , and the liquid medium I with a suitable density is selected according to the density of the waste mixed plastic particles to be separated.
进一步优选的方案中液体介质I选自醇水混合溶液,或者为自来水、去离子水、海水、蒸馏水中的至少一种,或者为氯化钠、硫酸钠、氯化钙、氯化钾、硝酸钾、硝酸钠中的至少一种的水溶液。In a further preferred scheme, the liquid medium I is selected from an alcohol-water mixed solution, or at least one of tap water, deionized water, seawater, and distilled water, or sodium chloride, sodium sulfate, calcium chloride, potassium chloride, nitric acid An aqueous solution of at least one of potassium and sodium nitrate.
优选的方案中根据待分离塑料的平均密度来选择合适的液体介质I,液体介质I的密度比轻组分塑料密度大,比重组分塑料密度小。液体介质I可以选择为密度接近1000kg/m3的自来水、去离子水、海水、蒸馏水中的至少一种;或者选择为密度在970~1000kg/m3之间的甲醇和/或乙醇的水溶液,或者选择为密度在1000~1200kg/m3之间的氯化钠、硫酸钠、氯化钙、氯化钾、硝酸钾、硝酸钠中至少一种的水溶液。In the preferred scheme, a suitable liquid medium I is selected according to the average density of the plastic to be separated, and the density of the liquid medium I is higher than that of light component plastics and lower than that of heavy component plastics. The liquid medium I can be selected as at least one of tap water, deionized water, seawater, and distilled water with a density close to 1000kg/ m3 ; or an aqueous solution of methanol and/or ethanol with a density of 970~1000kg/ m3 , Alternatively, it may be selected as an aqueous solution of at least one of sodium chloride, sodium sulfate, calcium chloride, potassium chloride, potassium nitrate and sodium nitrate with a density between 1000-1200 kg/ m3 .
优选的方案中重组分塑料颗粒加入到温度为70~100℃的液体介质II中进行表面处理30~180min。In a preferred solution, the heavy component plastic particles are added to the liquid medium II at a temperature of 70-100° C. for 30-180 minutes of surface treatment.
进一步优选的方案中液体介质II为自来水、去离子水、海水、蒸馏水、氯化钠溶液、硫酸钠溶液、氯化钙溶液、氯化钾溶液、硝酸钾溶液、硝酸钠溶液中的至少一种。液体介质II的pH为7左右。In a further preferred scheme, the liquid medium II is at least one of tap water, deionized water, seawater, distilled water, sodium chloride solution, sodium sulfate solution, calcium chloride solution, potassium chloride solution, potassium nitrate solution, and sodium nitrate solution . The pH of the liquid medium II is around 7.
优选的方案中经表面处理后的重组分塑料颗粒分散在浮选介质中,加入浮选剂进行浮选分离。In the preferred solution, the surface-treated heavy plastic particles are dispersed in the flotation medium, and a flotation agent is added for flotation separation.
优选的方案中浮选剂包括具有气泡效果的浮选剂和/或具有润湿效果的浮选剂。In a preferred solution, the flotation agent includes a flotation agent with a bubble effect and/or a flotation agent with a wetting effect.
进一步优选的方案中具有气泡效果的浮选剂为松油醇、甲基异丁基甲醇、α-萜烯醇、聚乙二醇中的至少一种。In a further preferred solution, the flotation agent with bubble effect is at least one of terpineol, methyl isobutyl carbinol, α-terpene alcohol, and polyethylene glycol.
进一步优选的方案中具有润湿效果的浮选剂为木质素磺酸盐、单宁酸、明胶、白雀树皮汁、纤维素、烷基聚氧乙烯醚、水玻璃、脂肪胺中的至少一种。In the further preferred scheme, the flotation agent with wetting effect is at least one of lignosulfonate, tannic acid, gelatin, sparrow bark juice, cellulose, alkyl polyoxyethylene ether, water glass, fatty amine A sort of.
进一步优选的方案中浮选剂按10~500mg/L的量加入到浮选介质中。最优选为按20~300mg/L的量加入到浮选介质中。In a further preferred scheme, the flotation agent is added to the flotation medium in an amount of 10-500 mg/L. Most preferably, it is added to the flotation medium in an amount of 20-300 mg/L.
进一步优选的方案中浮选介质为自来水、去离子水、海水、蒸馏水中的至少一种。In a further preferred solution, the flotation medium is at least one of tap water, deionized water, seawater, and distilled water.
进一步优选的方案中浮选分离时间为1~15min。In a further preferred solution, the flotation separation time is 1 to 15 minutes.
优选的方案中轻组分塑料包括聚乙烯和/或聚丙烯,重组分塑料中的不含极性基团的塑料包括含芳环的塑料,重组分塑料中的含极性基团的塑料包括含硫、氧、氮杂原子基团的塑料;重组分塑料占废旧混合塑料质量的1%~99%。不含极性基团的塑料如聚苯乙烯等。含极性基团的塑料为聚碳酸酯、聚酰胺等。In the preferred scheme, the light component plastics include polyethylene and/or polypropylene, the plastics without polar groups in the heavy component plastics include plastics containing aromatic rings, and the plastics containing polar groups in the heavy component plastics include Plastics containing sulfur, oxygen, and nitrogen heteroatom groups; heavy component plastics account for 1% to 99% of the mass of waste mixed plastics. Plastics without polar groups such as polystyrene, etc. Plastics containing polar groups are polycarbonate, polyamide, etc.
优选的方案中重组分塑料占废旧混合塑料质量的1%~99%。In a preferred solution, the heavy component plastics account for 1% to 99% of the mass of waste mixed plastics.
优选的方案中废旧混合塑料破碎成粒径为1~10mm的混合塑料颗粒。In a preferred scheme, waste and old mixed plastics are crushed into mixed plastic particles with a particle size of 1-10 mm.
优选的方案中破碎为冷冻破碎或机械破碎。In a preferred solution, crushing is freeze crushing or mechanical crushing.
进一步优选的方案中冷冻破碎是先将塑料进行冷冻处理后,立即进行机械破碎。In a further preferred solution, freeze crushing is to freeze the plastic first and then mechanically crush it immediately.
进一步优选的方案中机械破碎通过破碎机实现,同时在破碎过程中在破碎机中加入适量的水以保证塑料温度不大于40℃。In a further preferred solution, the mechanical crushing is realized by a crusher, and at the same time, an appropriate amount of water is added to the crusher during the crushing process to ensure that the temperature of the plastic is not greater than 40°C.
所述的破碎为颚式破碎机、旋回破碎机、冲击式破碎机或辊式破碎机。The crushing is jaw crusher, gyratory crusher, impact crusher or roller crusher.
进一步优选的方案中在浮选过程中通过搅拌方式促使塑料颗粒在浮选介质中分散均匀,搅拌速率为不大于100r/min。In a further preferred solution, the plastic particles are uniformly dispersed in the flotation medium by stirring during the flotation process, and the stirring rate is not greater than 100 r/min.
进一步优选的方案中在浮选过程中向浮选介质中通入适量空气以促进气泡产生,充气速率为1~800mL/min。In a further preferred solution, an appropriate amount of air is introduced into the flotation medium during the flotation process to promote the generation of air bubbles, and the inflation rate is 1-800 mL/min.
优选的方案中将废旧混合塑料先经过清洗去除表面油污和泥沙等非塑料污染物;清洗过程中可加入适量氢氧化钠或清洗剂以促进清洗效果。In the preferred solution, the waste and old mixed plastics are first cleaned to remove non-plastic pollutants such as surface oil and sediment; an appropriate amount of sodium hydroxide or cleaning agent can be added during the cleaning process to improve the cleaning effect.
优选的方案中经表面处理后的重组分塑料颗粒进行浮选之前采用水洗涤,可以用水冲洗冷却,或者用水浸泡5~60min。In a preferred solution, the surface-treated heavy plastic particles are washed with water before flotation, and can be rinsed and cooled with water, or soaked in water for 5-60 minutes.
本发明的废旧混合塑料分离的方法包括以下步骤:The method for separating waste and old mixed plastics of the present invention comprises the following steps:
步骤1:对废旧混合塑料进行清洗;清洗过程加入少量的氢氧化钠或清洗剂以促进清洗效果;Step 1: Clean the waste and old mixed plastics; add a small amount of sodium hydroxide or cleaning agent during the cleaning process to promote the cleaning effect;
步骤2:采用冷冻破碎或机械破碎将废旧混合塑料破碎成粒度为1~10mm的混合塑料颗粒;将废旧混合塑料先冷冻处理,再进行机械破碎,或者直接采用机械破碎,机械破碎过程中向破碎机中加入适量水以保证塑料的温度低于40℃;采用的破碎机械为颚式破碎机、旋回破碎机、冲击式破碎机或辊式破碎机;所述的废旧混合塑料中包含至少一种密度相对较小的轻组分塑料和至少两种密度相近且密度相对较大的重组分塑料,其中,重组分塑料中至少含有一种含杂极性基团的塑料和不含极性基团的塑料;Step 2: Use freeze crushing or mechanical crushing to crush the waste mixed plastics into mixed plastic particles with a particle size of 1-10mm; freeze the waste mixed plastics first, and then perform mechanical crushing, or directly use mechanical crushing, and the mechanical crushing process will be crushed Add an appropriate amount of water to the machine to ensure that the temperature of the plastic is lower than 40°C; the crushing machinery used is a jaw crusher, a gyratory crusher, an impact crusher or a roller crusher; the waste mixed plastic contains at least one Light component plastics with a relatively low density and at least two heavy component plastics with similar densities and relatively high densities, wherein the heavy component plastics contain at least one type of plastic containing heteropolar groups and plastics without polar groups plastic;
步骤3:将混合塑料颗粒加入到液体介质I中进行沉浮分离出轻组分塑料颗粒和重组分塑料颗粒,液体介质I根据实际待分离塑料的密度可以选择为密度接近1000kg/m3的自来水、去离子水、海水、蒸馏水中的至少一种;或者选择为密度在970~1000kg/m3之间的甲醇和/或乙醇的水溶液,或者选择为密度在1000~1200kg/m3之间的氯化钠、硫酸钠、氯化钙、氯化钾、硝酸钾、硝酸钠中至少一种的水溶液;Step 3: Add the mixed plastic particles into the liquid medium I for sinking and floating to separate the light component plastic particles and the heavy component plastic particles. The liquid medium I can be selected as tap water with a density close to 1000kg/ m3 according to the actual density of the plastic to be separated. At least one of deionized water, seawater, and distilled water; or an aqueous solution of methanol and/or ethanol with a density between 970 and 1000 kg/ m3 , or chlorine with a density between 1000 and 1200 kg/ m3 An aqueous solution of at least one of sodium chloride, sodium sulfate, calcium chloride, potassium chloride, potassium nitrate, and sodium nitrate;
步骤4:对沉浮分离所得的重组分塑料颗粒加入到70~100℃的液体介质II中进行表面处理30~180min,液体介质II为为自来水、去离子水、海水、蒸馏水、氯化钠溶液、硫酸钠溶液、氯化钙溶液、氯化钾溶液、硝酸钾溶液、硝酸钠溶液中的至少一种;Step 4: Add the heavy component plastic particles obtained from the sink-float separation into liquid medium II at 70-100°C for surface treatment for 30-180 minutes. The liquid medium II is tap water, deionized water, seawater, distilled water, sodium chloride solution, At least one of sodium sulfate solution, calcium chloride solution, potassium chloride solution, potassium nitrate solution, sodium nitrate solution;
步骤5:对表面处理后的重组分塑料颗粒采用自来水冲洗冷却,或者在重组分塑料颗粒在水中浸泡5~60min;Step 5: Rinse and cool the surface-treated heavy-component plastic particles with tap water, or soak the heavy-component plastic particles in water for 5-60 minutes;
步骤6:将重组分塑料颗粒分散在浮选介质中,加入浮选剂进行浮选分离;按10~500mg/L加入浮选剂,以1~800mL/min的速率鼓入空气,进行浮选分离1~15min,浮选出不含极性基团的塑料;浮选介质为自来水、去离子水、海水、蒸馏水中的至少一种;浮选剂为松油醇、甲基异丁基甲醇、α-萜烯醇和聚乙二醇、木质素磺酸盐、单宁酸、明胶、白雀树皮汁、纤维素、烷基聚氧乙烯醚、水玻璃、脂肪胺中的至少一种。Step 6: Disperse the heavy component plastic particles in the flotation medium, add flotation agent for flotation separation; add flotation agent at a rate of 10-500mg/L, blow air in at a rate of 1-800mL/min, and perform flotation Separation for 1-15 minutes, flotation to produce plastics without polar groups; flotation medium is at least one of tap water, deionized water, sea water, and distilled water; flotation agent is terpineol, methyl isobutyl carbinol , α-terpene alcohol and at least one of polyethylene glycol, lignosulfonate, tannic acid, gelatin, quebracho bark juice, cellulose, alkyl polyoxyethylene ether, water glass, fatty amine.
相对现有技术,本发明的有益效果在于:基于现有技术中对混合塑料难以实现多组分分离,本发明首次以浮沉分离和浮选分离方法相结合对混合塑料进行选择性分离,可以多种塑料同时分离,特别是对密度相近的混合塑料的分离。本发明在适当温度条件下对密度相近的塑料进行表面处理,使其中的聚苯烯等塑料能够结合选矿领域中的浮选法进行选择性富集分离。本发明方案对废旧塑料中的各种塑料分离效果好,回收率高;另外,本发明的工艺操作简单、成本低,具有很好的经济可行性,满足工业化应用。Compared with the prior art, the beneficial effect of the present invention lies in that: based on the fact that it is difficult to achieve multi-component separation of mixed plastics in the prior art, the present invention combines floating-sink separation and flotation separation methods for the first time to selectively separate mixed plastics, and can multi-component Simultaneous separation of two kinds of plastics, especially for the separation of mixed plastics with similar densities. The invention carries out surface treatment on the plastics with similar densities under appropriate temperature conditions, so that the plastics such as polystyrene can be selectively enriched and separated in combination with the flotation method in the mineral processing field. The solution of the invention has good separation effect on various plastics in waste plastics, and has a high recovery rate; in addition, the process of the invention is simple in operation, low in cost, has good economic feasibility, and satisfies industrial application.
具体实施方式detailed description
通过以下实施例进一步阐释本发明,实施例不以任何方式被解释成对本发明的范围强加限制。相反,应清楚理解,可以采取本领域的技术人员在阅读本文的描述之后可以看出的各种其他实施方案、修改及其等效物而不偏离本发明的精神和/或所附权利要求的范围。The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations on the scope of the present invention. On the contrary, it should be clearly understood that various other embodiments, modifications and their equivalents, which can be seen by those skilled in the art after reading the description herein, can be adopted without departing from the spirit of the invention and/or the spirit of the appended claims. scope.
实施例1Example 1
将含PC、PS和PP的混合塑料加入到含有少量清洗剂的自来水中清洗,然后采用塑料破碎机破碎,机械破碎过程中向破碎机中加入适量水以保证塑料的温度低于40℃,取3.2~4.0mm粒径的塑料颗粒30g(PC、PS和PP的质量比为1:1:1)加入到自来水中,PP塑料颗粒通过浮沉法从自来水上层分离出来,然后将PC和PS塑料颗粒加入到100℃的沸水中,处理70min,取出用水冷却后进行浮选,浮选条件为:200mg/L松油醇、浮选2min,充气速率为7.5mL/min,搅拌速率为100r/min。分离后PC的纯度达到86.42%,回收率达到91.86%;PS的纯度达到92.34%,回收率达到98.04%。Add mixed plastics containing PC, PS and PP to tap water containing a small amount of cleaning agent for cleaning, and then use a plastic crusher to crush it. During the mechanical crushing process, add an appropriate amount of water to the crusher to ensure that the temperature of the plastic is lower than 40°C. Add 30g of plastic particles with a particle size of 3.2 to 4.0mm (the mass ratio of PC, PS and PP is 1:1:1) into tap water, PP plastic particles are separated from the upper layer of tap water by floating and sinking, and then the PC and PS plastic particles Add it into boiling water at 100°C, treat it for 70 minutes, take it out and cool it with water, and then carry out flotation. The flotation conditions are: 200mg/L terpineol, flotation for 2 minutes, the aeration rate is 7.5mL/min, and the stirring rate is 100r/min. After separation, the purity of PC reached 86.42%, and the recovery rate reached 91.86%; the purity of PS reached 92.34%, and the recovery rate reached 98.04%.
实施例2Example 2
将含PC、PS和PE的混合塑料加入到含有少量清洗剂的自来水中清洗,然后在-10低温下冷冻,采用塑料破碎机破碎进行常规破碎,取3.2-4.0mm粒径的塑料颗粒30g(PC、PS和PE的质量比为1:1:1)加入到自来水中,PE塑料颗粒通过浮沉法从自来水上层分离出来,然后将PC和PS塑料颗粒加入到100℃的食盐水中,处理80min,取出用水冷却,后进行浮选,浮选条件为:35.1mg/L甲基异丁基甲醇、浮选4min,充气速率为7.5mL/min,搅拌速率为50r/min。分离后PC的纯度达到94.86%,PS的回收率达到98.04%。Add the mixed plastic containing PC, PS and PE to tap water containing a small amount of cleaning agent to clean, then freeze at -10°C, use a plastic crusher to crush it for conventional crushing, and take 30g of plastic particles with a particle size of 3.2-4.0mm ( The mass ratio of PC, PS and PE is 1:1:1) into tap water, PE plastic particles are separated from the upper layer of tap water by floating and sinking, and then PC and PS plastic particles are added to 100°C salt water for 80 minutes, Take it out and cool it with water, and then carry out flotation. The flotation conditions are: 35.1mg/L methyl isobutyl carbinol, flotation for 4min, the aeration rate is 7.5mL/min, and the stirring rate is 50r/min. After separation, the purity of PC reached 94.86%, and the recovery rate of PS reached 98.04%.
实施例3Example 3
将含ABS、PS和PP的塑料加入到含有少量氢氧化钠的自来水中清洗,然后采用塑料破碎机破碎,机械破碎过程中向破碎机中加入适量水以保证塑料的温度低于40℃,取3.2-4.0mm粒径的塑料颗粒30g(ABS、PS和PP的质量比为1:1:1)加入到海水中,PP塑料颗粒通过浮沉法从海水上层分离出来,然后将ABS和PS塑料颗粒加入到80℃的水介质中,处理110min,取出用水浸泡10分钟冷却后,进行浮选,浮选条件为:35.1mg/L木质素磺酸盐、浮选3min,充气速率为7.5mL/min,搅拌速率为50r/min。分离后ABS的纯度达到95.16%,PS的纯度达到91.37%,两种塑料的回收率达到91%。Add plastics containing ABS, PS and PP to tap water containing a small amount of sodium hydroxide for cleaning, and then use a plastic crusher to crush them. During the mechanical crushing process, add an appropriate amount of water to the crusher to ensure that the temperature of the plastics is lower than 40°C. Add 30g of plastic particles with a particle size of 3.2-4.0mm (the mass ratio of ABS, PS and PP is 1:1:1) into seawater, and the PP plastic particles are separated from the upper layer of seawater by floating and sinking, and then the ABS and PS plastic particles Add it into the water medium at 80°C, treat it for 110 minutes, take it out and soak it in water for 10 minutes to cool it down, and then carry out flotation. , the stirring rate is 50r/min. After separation, the purity of ABS reached 95.16%, the purity of PS reached 91.37%, and the recovery rate of the two plastics reached 91%.
实施例4Example 4
将含ABS、PS和PE的塑料加入到含有少量氢氧化钠的自来水中清洗,然后采用塑料破碎机破碎,机械破碎过程中向破碎机中加入适量水以保证塑料的温度低于40℃,取2.0-2.5mm粒径的塑料颗粒30g(ABS、PS和PE的质量比为5:1:1)加入到自来水中,PE塑料颗粒通过浮沉法从自来水上层分离出来,然后将ABS和PS塑料颗粒加入到75℃的沸水中,处理170min,取出冷却后进行浮选,浮选条件为:20mg/L烷基聚氧乙烯醚、浮选3min,充气速率为70mL/min,搅拌速率为100r/min。分离后ABS的纯度达到90.46%,PS的纯度达到92.57%,两种塑料的回收率达到89%。Add plastics containing ABS, PS and PE to tap water containing a small amount of sodium hydroxide for cleaning, and then use a plastic crusher to crush them. During the mechanical crushing process, add an appropriate amount of water to the crusher to ensure that the temperature of the plastics is lower than 40°C. Add 30g of plastic particles with a particle size of 2.0-2.5mm (the mass ratio of ABS, PS and PE is 5:1:1) into tap water, PE plastic particles are separated from the upper layer of tap water by floating and sinking, and then the ABS and PS plastic particles Add it into boiling water at 75°C, treat it for 170min, take it out and cool it, and then carry out flotation. . After separation, the purity of ABS reached 90.46%, the purity of PS reached 92.57%, and the recovery rate of the two plastics reached 89%.
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Families Citing this family (13)
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CN114800938A (en) * | 2021-05-10 | 2022-07-29 | 上海睿聚环保科技有限公司 | Sorting mode of recycled plastics and application thereof |
CN114131789A (en) * | 2021-11-05 | 2022-03-04 | 石家庄绿色再生资源有限公司 | Composite sorting method for mixed plastics |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4127572C1 (en) * | 1991-08-21 | 1993-03-11 | Kali Und Salz Ag, 3500 Kassel, De | |
DE4127574C1 (en) * | 1991-08-21 | 1993-03-11 | Kali Und Salz Ag, 3500 Kassel, De | |
JP3263013B2 (en) * | 1997-08-21 | 2002-03-04 | 川崎重工業株式会社 | Method and apparatus for separating resin waste |
CN1145534C (en) * | 2000-07-13 | 2004-04-14 | 中国石油化工股份有限公司 | Floatation separator of waste plastics |
JP2006281506A (en) * | 2005-03-31 | 2006-10-19 | Jfe Steel Kk | Treatment method of waste plastic |
KR100948490B1 (en) * | 2009-11-27 | 2010-03-18 | 서흥인테크(주) | The selection method recycling plastic |
CN101941255B (en) * | 2010-06-10 | 2013-07-31 | 甘肃大禹节水股份有限公司 | Water flotation regeneration process of agricultural waste plastics |
CN203125773U (en) * | 2013-01-31 | 2013-08-14 | 冯愚斌 | Flotation-type crushing separation cleaning system for waste plastics |
CN203125772U (en) * | 2013-01-31 | 2013-08-14 | 冯愚斌 | Rotational flow type waste plastic breaking, sorting and cleaning system |
CN203125774U (en) * | 2013-01-31 | 2013-08-14 | 冯愚斌 | Complete equipment for automatically separating plastic fragments with different densities |
CN103286000A (en) * | 2013-05-06 | 2013-09-11 | 四川长虹格润再生资源有限责任公司 | Method for sorting waste plastics |
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