CN106831390A - A kind of method of utilization waste PET film preparation monomer PTA - Google Patents
A kind of method of utilization waste PET film preparation monomer PTA Download PDFInfo
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- CN106831390A CN106831390A CN201611169966.3A CN201611169966A CN106831390A CN 106831390 A CN106831390 A CN 106831390A CN 201611169966 A CN201611169966 A CN 201611169966A CN 106831390 A CN106831390 A CN 106831390A
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- pta
- pet film
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention provides a kind of method of utilization waste PET film preparation monomer PTA, comprises the following steps：1) by waste PET film and EG according to 10~40%：60~90% mass ratio mixing, depolymerization reaction is carried out at 180~260 DEG C, obtains the BHET solution containing impurity；2) by step 1) the BHET solution that obtains decolourized at 70~100 DEG C, washed so that and the impurity mixed in BHET solution is able to tentatively remove；3) by through step 2) treatment obtained by BHET solution carry out centrifugal filtration, obtain impurity further removing BHET solution；4) by through step 3) the BHET solution obtained by treatment is hydrolyzed reaction in 260~300 DEG C of water vapour, obtains the mixed liquor of PTA and EG；5) by step 4) PTA that obtains carries out centrifugal filtration with EG mixed liquors, separates to obtain the PTA aqueous solution, the EG aqueous solution.The method can effectively remove the impurity such as the ink that contains in waste PET film, and process is simple can be obtained the PTA of high-purity.
Description
Technical field
It is more particularly to a kind of to utilize waste and old polyethylene terephthalate the present invention relates to the recovery process of waste or used plastics
(PET) method of film preparation PTA, belongs to waste or used plastics cycling and reutilization technical field of macromolecules.
Background technology
Waste and old polyethylene terephthalate (PET) film is primarily referred to as the waste PET film before printing or after printing
And the PET laminated films printed after compound with PP or PE.It is a large amount of due to containing in waste PET film during recycling
Ink (typically about 10~15wt%), intractability is big；On the other hand, waste PET film chemical strong inert, is difficult by air
Or microbial degradation, " white pollution " is easily caused, it is an important environmental problem urgently to be resolved hurrily.
At present, the recoverying and utilizing method for waste or used plastics PET film mainly has chemical degradation method or physical method.Its
In, for chemical degradation method, following problem is primarily present at present：Method and step is more, and required raw material type is more, easily produces secondary
Pollution, it is impossible to effective recycling.
The Chinese patent application of Publication No. CN101284777 discloses a kind of waste and old polyethylene terephthalate modeling
The method of material degraded production terephthalic acid (TPA) and ethanedioic acid, it is with soluble cobalt, manganese salt, zirconates, cerium salt and bromide, has
Machine alkali is catalyst (zirconates, cerium salt are co-catalyst), with paraxylene as pro-oxidant, it is with waste PET plastics and lazy
Property solvent mixes in proportion, 100 DEG C~350 DEG C of temperature and the pressure condition of 0.4~4.0MPA under, using containing oxygen molecule
Gas waste PET is carried out oxidative degradation production terephthalic acid (TPA) and ethanedioic acid.The method is prepared using waste PET plastics
During terephthalic acid (TPA), required step is more, and control parameter is more, increased production control difficulty；In addition, required raw material type
It is many, increased the difficulty that later separation is refined and recycles.
The Chinese patent application of Publication No. CN101456809 discloses a kind of method of disaggregation of waste and old PET, with waste and old
PET is raw material, and water is supercritical medium, in the supercritical state, to polyethylene terephthalate depolymerization, obtains depolymerization product
Thing is terephthalic acid (TPA) and ethylene glycol, and polyethylene terephthalate is 1: 5~1: 20 with the weight ratio of water, and de-polymerization temperature exists
Between 375 DEG C~450 DEG C, pressure is between 22.12MPA~50MPA.
How to provide a kind of being readily applied to production, and process is simple, economic utilization waste PET film preparation monomer
The method of PTA, particularly ink content waste PET film recycle and reuse method high, be China in environmental protection cause urgently
One of technology for making a breakthrough, it is the art technical problem urgently to be resolved hurrily to be also,
The content of the invention
The present invention is the deficiency for making up prior art presence, there is provided a kind of side of utilization waste PET film preparation monomer PTA
Method, the method can effectively remove the impurity such as the ink that contains in waste PET film, and process is simple, required raw material be few, cost
It is low, it is easy to which that large-scale application is in production, moreover it is possible to the PTA of high-purity is obtained.
The present invention is to reach its purpose, and the technical scheme of use is as follows：
A kind of method of utilization waste PET film preparation monomer PTA, comprises the following steps：
1) by waste PET film and EG according to 10~40%：60~90% mass ratio mixing, enters at 180~260 DEG C
Row depolymerization reaction, the depolymerization reaction time is preferably 40~60min, and the BHET solution containing impurity is obtained through depolymerization reaction；
2) by step 1) the BHET solution that obtains decolourized at 70~100 DEG C, washed so that mix in BHET solution
Impurity is able to tentatively remove；
3) by through step 2) treatment obtained by BHET solution carry out centrifugal filtration, obtain impurity further removing BHET it is molten
Liquid；
4) by through step 3) the BHET solution obtained by treatment is hydrolyzed reaction in 260~300 DEG C of water vapour, hydrolyzes
Reaction time is preferably 30~50min, and the mixed liquor of PTA and EG is obtained through hydrolysis；
5) by step 4) PTA that obtains carries out centrifugal filtration with EG mixed liquors, separates to obtain the PTA aqueous solution, the EG aqueous solution.
Preferably, step 3), step 5) described in centrifugal filtration be equipped with centrifugation filter cloth belt centrifuge in enter
OK, wherein, step 3) used by centrifugation filter cloth belt mesh number be 60~80 microns, step 5) used by centrifugation filter cloth belt mesh number
It is 20~30 microns；Centrifugation filter cloth belt according to preferred mesh number combines filtering, optimal filter effect can be reached, through coarse filtration
The removal of impurity effectively is gone, PTA products are filtrated to get through essence.
As a kind of specific embodiment, step 1) described in impurity include ink.
Used as a kind of specific embodiment, the shared mass ratio in waste PET film of the ink is 8~15%.
Used as a kind of specific embodiment, the waste PET film is the waste PET film being combined with PP and/or PE.
As a kind of specific embodiment, the PET containing more than 70% mass ratio in the waste PET film.
Preferably, step 2) in, the used decolorising agent of decolourizing is aluminum oxide, activated carbon, in diatomite at least
One kind, using preferred decolorising agent, decolorizing effect it is further preferred that.It is more highly preferred to, decolorising agent is with the mass ratio of waste PET film
2~4:1, decolouring duration control in 30~50min, under optimum condition, decolorizing effect preferably, removal efficiency can reach 90% with
On.
Preferably, step 2) in, the time used by the washing is 30~50min.
Preferably, water used in preparation process is electrical conductivity<1uscm (25 DEG C), metal ion content<
The deionized water of 0.001Eu/ml.
Preferably, also including step 6)：By step:5) the EG aqueous solution and the PTA aqueous solution for obtaining carry out rectifying respectively, point
EG of the purity more than 99%, PTA of the purity more than 99.5% are not obtained.
The technical scheme that the present invention is provided has the advantages that：
1st, the present invention is reacted by being carried out the chemical depolymerization of waste PET film under certain reaction condition from EG solvents,
Then the BHET solution containing impurity such as ink that depolymerization is obtained is carried out into decolouring washing process, centrifugal filtration, is removed most of
The impurity such as ink, then hydrolyze purification in water vapour and under certain reaction condition and obtain PTA, and utilization is circulated to EG；
Using the method for the present invention, the printing compound film recovery technology problem high of ink content present in this area can be solved, taken
Technical breakthrough was obtained, the PTA of high-purity was prepared for through chemical method.
2nd, the method that the present invention is provided, process is simple, required raw material type is few, does not result in secondary pollution, energy-conserving and environment-protective,
And low cost.Technology controlling and process is simple, it is easy to large-scale application.
3rd, the present invention can be direct plungeed into as raw material using PTA, PE obtained in waste PET film and used, and improve circulation
Value, without cumbersome refined recovery process.
Specific embodiment
Technical scheme is described further with reference to specific embodiment：
Embodiment 1
1) waste and old polyethylene terephthalate (PET) film and EG that will be collected into are by 20%：80% mass ratio
Example is added in depolymerization tank, and depolymerization reaction is carried out at a temperature of 220 DEG C, and the reaction time is 40min, after obtaining PET depolymerization
Low molecule solution B HET solution.The low molecule solution that this step is obtained is that impurity content is higher and ink is not de- with PET low molecules
The mixed liquor for removing.
2) by step 1) the BHET solution that obtains is added to decolouring water washing device, and in 90 DEG C of decolourings, decolorising agent used is oxygen
Change aluminium, decolorising agent is 2 with the mass ratio of waste PET film:1, a length of 30min during decolouring；30min is washed after decolouring by the beginning of impurity
Step removing, and ink is separated with PET low molecules, obtain the clean BHET solution of comparing, the low molecule solution that this step is obtained
For impurity content is fewer, and ink is separated after desolventing technology with PET low molecules.
3) by through step 2) treatment obtained by BHET solution through containing centrifugation filter cloth belt centrifuge carry out at centrifugal filtration
Reason, obtains the low molecule solution B HET solution of purer PET depolymerization.It is after being processed through centrifuge that ink and impurity is further
Removing, the mesh number selection that filter cloth bag is centrifuged is 60 microns.
4) by step 3) during the BHET slurries that obtain add hydrolytic decomposition pot, it is hydrolyzed in 280 DEG C of water vapours of temperature anti-
Should, the reaction time is 30min, obtains the mixed liquor of PTA and EG.
5) by step 4) PTA that obtains locates with EG mixed solutions in the high-precision centrifuge for containing centrifugation filter cloth bag
Reason, the precision that filter cloth bag is centrifuged is 20um, and PTA is separated with the aqueous solution of EG；
6) the EG aqueous solution that will 5) obtain separates water with EG through rectifying, obtains EG and pure water of the purity more than 99%；Will
Step 5) the PTA aqueous solution that obtains carries out rectifying and obtains PTA powder of the purity more than 99.5% using rectifier unit.
Embodiment 2
1) waste and old polyethylene terephthalate (PET) film and EG that will be collected into are by 30%：70% mass ratio
Example is added in depolymerization tank, and depolymerization reaction is carried out at a temperature of 240 DEG C, and the reaction time is 50min, after obtaining PET depolymerization
Low molecule solution B HET solution.The low molecule solution that this step is obtained is that impurity content is higher and ink is not de- with PET low molecules
The mixed liquor for removing.
2) by step 1) the BHET solution that obtains is added to decolouring water washing device, and in 80 DEG C of decolourings, decolorising agent used is to live
Property charcoal, decolorising agent consumption and waste PET film mass ratio be 3:1, a length of 40min during decolouring；Washing 50min after decolouring will be miscellaneous
Matter is tentatively removed, and ink is separated with PET low molecules, obtains the clean low molecule BHET solution of comparing, what this step was obtained
Low molecule solution is that impurity content is fewer, and ink is separated after desolventing technology with PET low molecules.
3) by through step 2) treatment obtained by BHET solution through containing centrifugation filter cloth belt centrifuge carry out at centrifugal filtration
Reason, obtains the low molecule solution B HET solution of purer PET depolymerization.It is after being processed through centrifuge that ink and impurity is further
Removing, the mesh number selection that filter cloth bag is centrifuged is 80 microns.
4) by step 3) during the BHET slurries that obtain add hydrolytic decomposition pot, it is hydrolyzed in 270 DEG C of water vapours of temperature anti-
Should, the reaction time is 40min, obtains the mixed liquor of PTA and EG.
5) by step 4) PTA that obtains and EG mixed liquors in the high-precision centrifuge treatment containing centrifugation filter cloth bag, from
The precision of heart filter cloth bag is 20um, and PTA is separated with the aqueous solution of EG.
6) the EG aqueous solution that will 5) obtain separates water with EG through rectifying, obtains EG and pure water of the purity more than 99%；Will
Step 5) the PTA aqueous solution that obtains carries out rectifying and obtains PTA powder of the purity more than 99.5% using rectifier unit.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not done to the present invention, therefore
All contents without departing from technical solution of the present invention, any simply repair according to technical spirit of the invention to made for any of the above embodiments
Change, equivalent variations and modification, still fall within the range of technical solution of the present invention.
Claims (10)
1. a kind of method of utilization waste PET film preparation monomer PTA, it is characterised in that comprise the following steps：
1) by waste PET film and EG according to 10~40%：60~90% mass ratio mixing, is solved at 180~260 DEG C
Poly- reaction, obtains the BHET solution containing impurity；
2) by step 1) the BHET solution that obtains decolourized at 70~100 DEG C, washed so that the impurity mixed in BHET solution
It is able to tentatively remove；
3) by through step 2) treatment obtained by BHET solution carry out centrifugal filtration, obtain impurity further removing BHET solution；
4) by through step 3) the BHET solution obtained by treatment is hydrolyzed reaction in 260~300 DEG C of water vapour, obtains PTA
With the mixed liquor of EG；
5) by step 4) PTA that obtains carries out centrifugal filtration with EG mixed liquors, separates to obtain the PTA aqueous solution, the EG aqueous solution.
2. method according to claim 1, it is characterised in that step 3), step 5) described in centrifugal filtration be to match somebody with somebody
Have centrifugation filter cloth belt centrifuge in carry out, wherein, step 2) used by centrifugation filter cloth belt mesh number be 60~80 microns, step
It is rapid 5) used by centrifugation filter cloth belt mesh number be 20~30 microns.
3. method according to claim 1, it is characterised in that step 1) described in impurity include ink.
4. method according to claim 3, it is characterised in that the shared mass ratio in waste PET film of the ink
It is 8~15%.
5. method according to claim 1, it is characterised in that the waste PET film is and that PP and/or PE is compound is useless
Old PET film.
6. method according to claim 5, it is characterised in that contain more than 70% mass ratio in the waste PET film
PET.
7. method according to claim 1, it is characterised in that step 2) in, the used decolorising agent that decolourizes is oxygen
Change aluminium, activated carbon, at least one in diatomite；Preferably, decolorising agent and the mass ratio of waste PET film are 2~4:1,
Decolouring duration is controlled in 30~50min.
8. method according to claim 1, it is characterised in that step 2) in, the washing time used is 30~50min.
9. method according to claim 1, it is characterised in that water used is electrical conductivity in preparation process<1us·cm
(25 DEG C), metal ion content<The deionized water of 0.001Eu/ml.
10. method according to claim 1, it is characterised in that also including step 6)：By step 5) the EG aqueous solution that obtains
Rectifying is carried out respectively with the PTA aqueous solution, respectively obtains EG of the purity more than 99%, PTA of the purity more than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169966.3A CN106831390A (en) | 2016-12-16 | 2016-12-16 | A kind of method of utilization waste PET film preparation monomer PTA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169966.3A CN106831390A (en) | 2016-12-16 | 2016-12-16 | A kind of method of utilization waste PET film preparation monomer PTA |
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| Publication Number | Publication Date |
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| CN106831390A true CN106831390A (en) | 2017-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611169966.3A Withdrawn CN106831390A (en) | 2016-12-16 | 2016-12-16 | A kind of method of utilization waste PET film preparation monomer PTA |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128635A (en) * | 2019-06-10 | 2019-08-16 | 中塑联新材料科技湖北有限公司 | A kind of method that useless PET film electronation prepares PBT raw material |
| CN110204781A (en) * | 2019-06-17 | 2019-09-06 | 中塑联新材料科技湖北有限公司 | A kind of method of terylene waste spinning depolymerization filtering decoloration |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW242150B (en) * | 1992-05-18 | 1995-03-01 | Simon Michael West | |
| CN1498914A (en) * | 2002-09-30 | 2004-05-26 | 株式会社爱维塑 | Process for removing coloring substance from ethanediol decomposition generated solution of polyester |
| CN104357938A (en) * | 2014-11-03 | 2015-02-18 | 东华大学 | Preparation method of regenerated polyester fibers |
-
2016
- 2016-12-16 CN CN201611169966.3A patent/CN106831390A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW242150B (en) * | 1992-05-18 | 1995-03-01 | Simon Michael West | |
| CN1498914A (en) * | 2002-09-30 | 2004-05-26 | 株式会社爱维塑 | Process for removing coloring substance from ethanediol decomposition generated solution of polyester |
| CN104357938A (en) * | 2014-11-03 | 2015-02-18 | 东华大学 | Preparation method of regenerated polyester fibers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128635A (en) * | 2019-06-10 | 2019-08-16 | 中塑联新材料科技湖北有限公司 | A kind of method that useless PET film electronation prepares PBT raw material |
| CN110204781A (en) * | 2019-06-17 | 2019-09-06 | 中塑联新材料科技湖北有限公司 | A kind of method of terylene waste spinning depolymerization filtering decoloration |
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Application publication date: 20170613 |
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