CN109810284A - A method of 12 waste material of nylon is dissolved using composite solvent system - Google Patents
A method of 12 waste material of nylon is dissolved using composite solvent system Download PDFInfo
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- CN109810284A CN109810284A CN201910107877.3A CN201910107877A CN109810284A CN 109810284 A CN109810284 A CN 109810284A CN 201910107877 A CN201910107877 A CN 201910107877A CN 109810284 A CN109810284 A CN 109810284A
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- nylon
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- composite solvent
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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 relates to a kind of method using composite solvent system dissolution 12 waste material of nylon, specifically includes the following steps: S1,12 waste material of nylon is added in composite solvent system, stirring and dissolving；To 60-90 DEG C, constant temperature water bath keeps 2-5h, dissolves 12 waste material of nylon sufficiently for S2, heating reaction system；S3, solution after reaction is centrifuged, deionized water is added into supernatant liquor, the precipitating of nylon 12 is precipitated；S4, the precipitating vacuum drying of nylon 12 is completely removed solvent and obtains 12 powder of nylon.The simple process of 12 waste recovery of nylon dissolution provided by the invention is easily implemented, and solvent for use safety and environmental protection is reusable, and low in cost, dissolved efficiency is high, convenient for universal and popularization.
Description
Technical field
The present invention relates to solid waste resource recoveries to be recycled field, utilizes composite solvent system more particularly to a kind of
Dissolve the method for 12 waste material of nylon.
Background technique
12 chemistry of nylon is commonly called as nylon 12, as a kind of hemicrystalline high polymer, compares in other nylon types,
, water absorption rate low with melting temperature and the relatively low characteristic of molding shrinkage, have good comprehensive mechanical property, are widely used in
The numerous areas such as auto electric equipment component, optical fiber jacket, Ordnance Store.With the fast development of 3D printing technique in recent years,
Nylon 12 has broad application prospects as one of 3D printing primary raw material.However since 12 service life of nylon is short, it is easy to
Aging is not easy the disadvantages of voluntarily degrading, it is easy to the accumulation of 12 waste material of nylon is caused, it will be to soil if it is directly arbitrarily abandoned
Earth, atmosphere, water source etc. cause seriously to pollute, and directly threaten various the animals and plants even existence of the mankind, cause environmental problem prominent.
It therefore, is a great problem of current urgent need to resolve how by the leftover pieces generated in use process, defect ware recycling and reusing；
Secondly, nylon material belongs to the higher macromolecular material of calorific value, recycling has feasibility, on the other hand can also give full play to
Its inherent value protects environment, therefore it is significant to study its High efficiency recovery；Finally, the recovery processing skill of 12 waste material of nylon
Art research, which comprehensively utilizes it, to be had a direct impact, and also illustrates that the technology has very strong popularization practicability.
The method of dissolution 12 waste material of nylon is mainly dissolved using organic alcohols at present, at low temperature almost according to nylon material
Insoluble in the solvent, and under higher temperature and pressure condition can compared with the characteristic of good dissolving, conventionally used alcohols solvent such as methanol,
Ethyl alcohol, ethylene glycol etc..104163929 A of CN relates to the dissolution and preparation method of a kind of nylon 12 material, and this method is by nylon
12 materials and ethyl alcohol are put into autoclave, are stirred and are passed through nitrogen protection, be heated to 130-160 DEG C, and keep the temperature 2-3h,
So that nylon 12 material dissolves.This method can be such that nylon 12 material quickly dissolves, solvent for use Environmental Safety, at low cost,
It is reusable, but need to carry out at high temperature under high pressure, and the solubility of 12 waste material of nylon is restricted, dissolved efficiency is not high.Closely
There is 102492155 A of patent CN to disclose a kind of method using the waste and old nylon 12 of ion liquid dissolving again within several years, by waste nylon 6
Dragon 12 is dissolved in ionic liquid, dissolves 3-18h through oil bath high-temperature stirring, and after cooling plus deionized water is precipitated.The invention provides
Method apparatus and process it is simple, solvent is recyclable, but ionic liquid is generally more toxic, and higher cost, dissolution
It takes a long time, to limit its large-scale application.
Summary of the invention
It is an object of the invention to overcome exclusive use organic alcohols in the prior art or ion liquid dissolving nylon 12 useless
The shortcomings that material, provides a kind of method using composite solvent system dissolution 12 waste material of nylon, and this method is simply easily implemented, and economy has
Effect, environmental-friendly, low energy consumption, and big to the recovery processing amount of 12 waste material of nylon, and dissolved efficiency is high.
In order to solve the above technical problems, the technical scheme is that as following manner is realized:
A method of 12 waste material of nylon being dissolved using composite solvent system, is specifically comprised the following steps:
S1,12 waste material of nylon is added in composite solvent system, stirring and dissolving；
Preferably, 12 waste material of nylon is in the Industry Waste powder of underburnt state during 3D printing technique, main
Wanting ingredient is nylon 12, structural formula are as follows: H- [NH (CH2)11]n-OH。
Preferably, 12 waste material of nylon and the solid-to-liquid ratio of double solvents of being added is 1:6-1:15.
Preferably, the volume proportion of the double solvents is formic acid 5-28%, hydrochloric acid 1-10%, acetic acid 25-35%, residue
For deionized water.
Preferably, the speed of agitator is 120-200r/min.
S2, heating reaction system keep 2-5h through constant temperature water bath, dissolve 12 waste material of nylon sufficiently to 60-90 DEG C；
S3, solution after reaction is centrifuged, lower layer's insoluble matter (additive), which is collected, to be recycled, and is added in supernatant liquor
Enter deionized water and the precipitating of nylon 12 is precipitated；
Preferably, the centrifugal rotational speed is 3000-4000r/min, centrifugation time 5-15min.
S4, it the precipitating vacuum drying of nylon 12 is completely removed into solvent obtains 12 powder of nylon, liquids recovery is reused.
Preferably, it is 80-100 DEG C that the nylon 12, which precipitates vacuum drying temperature, drying time 8-10h.
Beneficial effects of the present invention:
Compared with prior art, the present invention utilizes formic acid, hydrochloric acid, acetic acid to form composite solvent system dissolution nylon 12 for the first time
Waste material, is better than intermolecular active force according to 12 molecule of nylon and the hydrogen bond action between solvent and what Compound-acid generated cooperates with effect
It answers, 12 macromolecular of nylon is made gradually to dissolve dispersion in a solvent.Solvent molecule initially enters the amorphous of nylon 12 in course of dissolution
Area, opens the intermolecular hydrogen bond of amorphous area, and amorphous area starts to dissolve；Crystalline region crystal solvent molecule continue effect under, gradually
Disintegrate, is dissolved in conjunction with solvent molecule.In addition, solid-to-liquid ratio of the present invention by adjusting nylon 12 waste material and solvent, guarantees
Increase reaction system volume when certain acid concentration, expand the contact area of nylon 12 molecule and solvent molecule, improves dissolved efficiency；
Simultaneously under the premise of reducing solvent volatilization loss, solution temperature is improved, solvent molecule enhances 12 crystalline region hydrogen bond action of nylon,
So that dissolution rate further increases, dissolved efficiency can reach 80-95%.
Dicyandiamide solution used herein may be recovered reuse, and compared with the prior art, the present invention is without height
High-temperature high-pressure apparatus, technological operation is simple, and low energy consumption, selects solvent cheap, environment friendly and pollution-free, being capable of high-efficiency dissolution nylon 12
Waste material is conducive to the recycling for protecting environment and resource.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
It is process object to be in the Industry Waste powder of underburnt state in selective laser sintering process, through detecting, ingredient is such as
Under: nylon 12 (nylon 12) weight ratio about 95%, silica accounts for about 5%.12 waste material of nylon is pressed with double solvents
Solid-to-liquid ratio 1:8 is added in three-necked flask, wherein the volume proportion of double solvents be formic acid 5%, hydrochloric acid 3%, acetic acid 25%,
Remaining as water.It using magnetic stirrer, is stirred evenly with 150r/min revolving speed, heating in water bath for reaction system is permanent to 60 DEG C
Warm stirring and dissolving 3h.10min, centrifugal rotational speed 4000r/min, lower silicon dioxide silicon are centrifuged to mixed liquor after reaction
Insoluble matter, which is collected, to be recycled, and isometric deionized water is added in supernatant liquor, the precipitating of nylon 12, liquid solvent recycling weight is precipitated
It is multiple to use.It is dry using vacuum drier, 90 DEG C of dry 10h are set, and the dissolution rate of recovery of final 12 waste material of nylon is
81.37%.
Embodiment 2
It is process object to be in the Industry Waste powder of underburnt state in selective laser sintering process, through detecting, ingredient is such as
Under: nylon 12 (nylon 12) weight ratio about 95%, silica accounts for about 5%.12 waste material of nylon is pressed with double solvents
Solid-to-liquid ratio 1:12 is added in three-necked flask, wherein the volume proportion of double solvents is formic acid 10%, hydrochloric acid 6%, acetic acid
30%, remaining as water.It using magnetic stirrer, is stirred evenly with 150r/min revolving speed, heating in water bath for reaction system to 70
DEG C, constant temperature stirring and dissolving 4h.10min, centrifugal rotational speed 4000r/min, lower part two are centrifuged to mixed liquor after reaction
Silica insoluble matter, which is collected, to be recycled, and isometric deionized water is added in supernatant liquor, the precipitating of nylon 12, liquid solvent is precipitated
Recycling is reused.It is dry using vacuum drier, 90 DEG C of dry 10h are set, and the dissolution rate of recovery of final 12 waste material of nylon is
86.84%.
Embodiment 3
It is process object to be in the Industry Waste powder of underburnt state in selective laser sintering process, through detecting, ingredient is such as
Under: nylon 12 (nylon 12) weight ratio about 95%, silica accounts for about 5%.12 waste material of nylon is pressed with double solvents
Solid-to-liquid ratio 1:15 is added in three-necked flask, wherein the volume proportion of double solvents is formic acid 15%, hydrochloric acid 10%, acetic acid
35%, remaining as water.It using magnetic stirrer, is stirred evenly with 200r/min revolving speed, heating in water bath for reaction system to 80
DEG C, constant temperature stirring and dissolving 4h.10min, centrifugal rotational speed 4000r/min, lower part two are centrifuged to mixed liquor after reaction
Silica insoluble matter, which is collected, to be recycled, and isometric deionized water is added in supernatant liquor, the precipitating of nylon 12, liquid solvent is precipitated
Recycling is reused.It is dry using vacuum drier, 80 DEG C of dry 10h are set, and the dissolution rate of recovery of final 12 waste material of nylon is
91.15%.
Embodiment 4
It is process object to be in the Industry Waste powder of underburnt state in selective laser sintering process, through detecting, ingredient is such as
Under: nylon 12 (nylon 12) weight ratio about 95%, silica accounts for about 5%.12 waste material of nylon is pressed with double solvents
Solid-to-liquid ratio 1:12 is added in three-necked flask, wherein the volume proportion of double solvents is formic acid 25%, hydrochloric acid 10%, acetic acid
35%, remaining as water.It using magnetic stirrer, is stirred evenly with 200r/min revolving speed, heating in water bath for reaction system to 80
DEG C, constant temperature stirring and dissolving 3h.10min, centrifugal rotational speed 4000r/min, lower part two are centrifuged to mixed liquor after reaction
Silica insoluble matter, which is collected, to be recycled, and isometric deionized water is added in supernatant liquor, the precipitating of nylon 12, liquid solvent is precipitated
Recycling is reused.It is dry using vacuum drier, 90 DEG C of dry 10h are set, and the dissolution rate of recovery of final 12 waste material of nylon is
95.07%.
It above are only several specific embodiments of the invention, since the source for generating 12 waste material of nylon is different,
Under the premise of essence of the invention and attached claim scope, some parameters of the invention can suitably be adjusted
It is whole, to adapt to particular situation.But the design concept of the present invention is not limited to this, all non-to present invention progress using this design
Substantive change, should all belong to behavior that violates the scope of protection of the present invention.
Claims (7)
1. a kind of method using composite solvent system dissolution 12 waste material of nylon, which comprises the following steps:
S1,12 waste material of nylon is added in composite solvent system, stirring and dissolving；
S2, heating reaction system keep 2-5h through constant temperature water bath, dissolve 12 waste material of nylon sufficiently to 60-90 DEG C；
S3, solution after reaction is centrifuged, lower layer's insoluble matter (additive), which is collected, to be recycled, and is added and is gone in supernatant liquor
Ionized water is precipitated nylon 12 and precipitates；
S4, it the precipitating vacuum drying of nylon 12 is completely removed into solvent obtains 12 powder of nylon, liquids recovery is reused.
2. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
12 waste material of nylon is in the Industry Waste powder of underburnt state during 3D printing technique, and main component is poly- 12
Lactams, structural formula are as follows: H- [NH (CH2)11]n-OH。
3. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
The solid-to-liquid ratio that 12 waste material of nylon and double solvents are added in the step S1 is 1:6-1:15.
4. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
In the step S1 volume proportion of double solvents be formic acid 5-28%, hydrochloric acid 1-10%, acetic acid 25-35%, remaining as go from
Sub- water.
5. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
Speed of agitator is 120-200r/min in the step S1.
6. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
Centrifugal rotational speed is 3000-4000r/min, centrifugation time 5-15min in the step S3.
7. a kind of method using composite solvent system dissolution 12 waste material of nylon according to claim 1, which is characterized in that
It is 80-100 DEG C that nylon 12, which precipitates vacuum drying temperature, in the step S4, drying time 8-10h.
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| CN201910107877.3A CN109810284A (en) | 2019-02-02 | 2019-02-02 | A method of 12 waste material of nylon is dissolved using composite solvent system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423377A (en) * | 2019-08-27 | 2019-11-08 | 上海松沅环境修复技术有限公司 | A kind of preparation method of high-purity nylon reworked material |
| CN111607123A (en) * | 2020-05-15 | 2020-09-01 | 宁波坚锋新材料有限公司 | Method for recovering nylon/polyolefin composite membrane by using ionic liquid |
| CN111892743A (en) * | 2020-06-30 | 2020-11-06 | 金发科技股份有限公司 | Polyamide recovery process and polyamide obtained by recovery process |
| CN115055484A (en) * | 2022-06-25 | 2022-09-16 | 共享智能装备有限公司 | Waste recovery method, waste recovery device and waste recovery system |
| CN115233455A (en) * | 2022-09-23 | 2022-10-25 | 江苏恒力化纤股份有限公司 | Method for preparing full-nylon composite coating fabric from nylon 6 waste silk |
| CN115558155A (en) * | 2022-10-28 | 2023-01-03 | 宁波坚锋新材料有限公司 | Method for preparing high-purity PA6 reclaimed material from fishing net wire reclaimed material and PA6 reclaimed material |
| CN115612286A (en) * | 2021-07-12 | 2023-01-17 | 中广核俊尔(浙江)新材料有限公司 | PA6 cloth reclaimed material and preparation method thereof |
| WO2024074794A1 (en) | 2022-10-05 | 2024-04-11 | Arkema France | Method for recycling a used polyamide composition |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423377A (en) * | 2019-08-27 | 2019-11-08 | 上海松沅环境修复技术有限公司 | A kind of preparation method of high-purity nylon reworked material |
| CN111607123A (en) * | 2020-05-15 | 2020-09-01 | 宁波坚锋新材料有限公司 | Method for recovering nylon/polyolefin composite membrane by using ionic liquid |
| CN111892743A (en) * | 2020-06-30 | 2020-11-06 | 金发科技股份有限公司 | Polyamide recovery process and polyamide obtained by recovery process |
| WO2022001054A1 (en) | 2020-06-30 | 2022-01-06 | 金发科技股份有限公司 | Polyamide recycling process and polyamide obtained by recycling process |
| CN115612286A (en) * | 2021-07-12 | 2023-01-17 | 中广核俊尔(浙江)新材料有限公司 | PA6 cloth reclaimed material and preparation method thereof |
| CN115612286B (en) * | 2021-07-12 | 2024-05-03 | 中广核俊尔(浙江)新材料有限公司 | PA6 cloth reworked material and preparation method thereof |
| CN115055484A (en) * | 2022-06-25 | 2022-09-16 | 共享智能装备有限公司 | Waste recovery method, waste recovery device and waste recovery system |
| CN115233455A (en) * | 2022-09-23 | 2022-10-25 | 江苏恒力化纤股份有限公司 | Method for preparing full-nylon composite coating fabric from nylon 6 waste silk |
| CN115233455B (en) * | 2022-09-23 | 2023-01-31 | 江苏恒力化纤股份有限公司 | Method for preparing full-nylon composite coating fabric from nylon 6 waste silk |
| WO2024074794A1 (en) | 2022-10-05 | 2024-04-11 | Arkema France | Method for recycling a used polyamide composition |
| FR3140628A1 (en) | 2022-10-05 | 2024-04-12 | Arkema France | Process for recycling a used polyamide composition |
| CN115558155A (en) * | 2022-10-28 | 2023-01-03 | 宁波坚锋新材料有限公司 | Method for preparing high-purity PA6 reclaimed material from fishing net wire reclaimed material and PA6 reclaimed material |
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