CN105712833A - Method for preparing p-xylene from waste PET (polyethylene glycol terephthalate) through hydrogenation degradation - Google Patents
Method for preparing p-xylene from waste PET (polyethylene glycol terephthalate) through hydrogenation degradation Download PDFInfo
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- CN105712833A CN105712833A CN201610205768.1A CN201610205768A CN105712833A CN 105712833 A CN105712833 A CN 105712833A CN 201610205768 A CN201610205768 A CN 201610205768A CN 105712833 A CN105712833 A CN 105712833A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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Abstract
The invention relates to a preparation method of p-xylene. P-xylene is prepared from a macromolecular polymer, namely, waste PET through high-temperature hydrogenation degradation with RuSnPt as a catalyst. The preparation method comprises specific steps as follows: the RuSnPt catalyst and PET are added to a high-pressure kettle in the mass ratio being 1%-20%, hydrogen is introduced under the pressure of 3-7 MPa at the room temperature, and the mixture is subjected to a reaction at the temperature of 240-350 DEGC for 3-13 h. The high-pressure kettle is washed with a solvent after the reaction ends, PET and the catalyst which are not decomposed are removed, a product is separated and purified, and p-xylene is obtained. The reaction condition is easy to control, operation is simple and convenient, no solvents are used in the reaction, post-treatment is simple, and the yield and the purity of p-xylene are high. Besides, a new method for preparing p-xylene is developed, a new direction is provided for resource reutilization of waste PET, and the preparation method has a great significance in environment protection and sustainable development.
Description
Technical field
The present invention relates to the recovery degraded of high molecular polymer and technical field of catalytic hydrogenation, specifically refer to a kind of method being prepared xylol by waste PET hydrogenation degraded.
Technical background
Polyethylene terephthalate (PET) is a kind of excellent polyester material, there is the combination properties such as high intensity, high rigidity, heat-resist, excellent dimensional stability and chemical proofing, be widely used in the fields such as carafe, fiber, thin film, chip base and electrical apparatus insulation material with the performance of its excellence.Due to stable chemical nature, this is difficult to be degraded in nature, and along with whole world PET yield and consumption figure increase rapidly, the process problem of waste PET becomes increasingly conspicuous.Therefore, the recovery of waste PET is subject to increasing attention with resource recycling in recent years.
The recovery method of waste PET is mainly physiochemical mutagens method and chemical recycling.Physiochemical mutagens method refers to by cutting off, pulverize, adding the operations such as heat fusing, the recycle utilization that waste or used plastics is reprocessed.Although physiochemical mutagens technology is reduced investment outlay, processing cost is cheap, but the performance of various regenerated plastics is greatly lowered than new material, and containing a large amount of impurity, generally can only demote use, it is unsuitable for manufacture packaging material for food, reclaim number of repetition limited simultaneously, finally must seek other way and process.Chemical recycling is exactly that depolymerization reaction occurs PET polyester under the effect of thermally and chemically reagent, generates monomer or other chemicals such as low-molecular-weight product such as TPA (p-phthalic acid), DMT (dimethyl terephthalate (DMT)), BHET (ethylene glycol terephthalate) and EG (ethylene glycol).Product is separated, after purification can again as producing the monomer of polyester or synthesizing the raw material of other chemical products and be reused, it is achieved thereby that the recycling of resource.
PET chemical recycling mainly has three kinds of techniques: Hydrolyze method, alcoholysis method and ammonolysis process.Current industrialized main method is Hydrolyze method and alcoholysis method.It is p-phthalic acid (TPA) and ethylene glycol (EG) that Hydrolyze method refers to PET water solution in different acid-alkali mediums by High Temperature High Pressure.Owing to TPA and EG is directly synthesized one of the important method that the technique of PET polyester is production of polyester so that Hydrolyze method reclaims waste PET and receives significant attention.But severe reaction conditions, equipment requirements is high, not easily realize large-scale production.Alcoholysis method refer to PET under an appropriate temperature and pressure conditions with alcohol generation ester exchange reaction, thus the method obtaining corresponding monomeric ester and ethylene glycol.Conventional alcohol has methanol, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol and hexanediol.But it is low to still suffer from reaction rate, product separation process is complicated, and degradation solution processes and catalyst reclaims the shortcomings such as difficulty.
Xylol, i.e. PX, it it is important aromatic hydrocarbon product, it is mainly used for producing purified terephthalic (TPA) and dimethyl terephthalate (DMT) (DMT), ethylene glycol terephthalate, mutual-phenenyl two acid bromide two alcohol ester can be obtained for raw material with the two, thus producing polyester fiber and polyester plastics, it it is one of important petrochemical industry Organic Ingredients.In addition xylol is also used as producing the raw material of medicine, spice, ink etc., of many uses.Developing rapidly recently as related industry, causes the growth rapidly of xylol demand, gradually forms the situation that supply falls short of demand.Having data to show, by 2016, the domestic demand to PX was estimated to be up to 25,050,000 tons, and wherein import volume accounts for more than 40%.Therefore, in great demand to PX of domestic market.
Xylol is generally mixed in various aroamtic hydrocarbon raw material, forms aromatic hydrocarbons mixture.It is the reformate and drippolene that obtain through catalytic reforming and catalytic cracking with oil at first, and the aromatic hydrocarbons mixture that coal liquefaction gas and coal gasification process prepare is raw material, obtains through extracting and separation.But the method process is loaded down with trivial details, the xylol limits throughput obtained, it is impossible to meet the high speed development demand of actual production.
In today that petroleum resources day is becoming tight, with waste PET for raw material, by hydrogenation catalyst degraded preparation PX, not only simplify operating process, and solvent-free use in reacting, post processing is simple, and the yield of xylol and purity are also higher.Meanwhile, developing the new method preparing xylol, the resource recycling for waste PET provides new direction simultaneously, and environmental conservation and sustainable development is significant.
Summary of the invention
It is an object of the invention to provide a kind of method being prepared PX by waste PET hydrogenation degraded.The method has not yet to see all reports.This method solve a difficult problem for waste PET recycling, provide a new approach for the recycling of waste PET, also provide new method for preparing xylol simultaneously, environmental conservation and sustainable development is significant.
The reaction expression of the present invention is:
The process of the present invention is waste PET to be hydrogenated with degraded under the effect of catalyst prepare xylol.
Specifically: be placed in autoclave with PET by certain mass ratio by catalyst, under room temperature, be filled with hydrogen, a period of time is reacted after being heated to reaction temperature, reaction uses solvent clean autoclave after terminating, removing undecomposed PET and catalyst, product, through separating and purification, obtains xylol.
As it has been described above, the catalyst adopted is RuSnX catalyst, wherein X is the 3rd component.
As mentioned above, it is characterised in that, described 3rd component is the one in Pt, Pd, Co, Ni or Rh.
As mentioned above, it is characterised in that, this reaction can carry out in one or several the mixture in hexamethylene, normal hexane, dioxane, oxolane.
As mentioned above, it is characterised in that, this reaction carries out under condition of no solvent.
As mentioned above, it is characterised in that, catalyst and PET mass ratio are 1%～20%.
As it has been described above, the Hydrogen Vapor Pressure being filled with under room temperature is 3～7MPa, reaction temperature is 240～350 DEG C, and the response time is 3～13h.
As mentioned above, it is characterised in that, the Hydrogen Vapor Pressure being filled with under room temperature is preferably 4～6MPa, and reaction temperature is preferably 280～320 DEG C, and the response time is preferably 7～11h.
As mentioned above, it is characterised in that, reaction can be one or several the mixture in methanol, ethanol, acetone, ether for cleaning the solvent of autoclave after terminating.
After reaction terminates, the degradation rate of PET is pressed formula (1) and is calculated.
Product is analyzed by gas chromatograph, and the selectivity of PX adopts area normalization to calculate.
Detailed description of the invention
By following example, the specific embodiment of the present invention is described and the present invention is further illustrated.And, the present invention is not limited in following embodiment, and when technology category belonging to front and back, change is included in the technical scope of the present invention.
Embodiment 1.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSn catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 280 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 78.4%, and the selectivity of PX is 39.5%.
Embodiment 2.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 240 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 26.4%, and the selectivity of PX is 18.5%.
Embodiment 3.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 280 DEG C, reacts 13h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 100%, and the selectivity of PX is 92.9%.
Embodiment 4.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 300 DEG C, reacts 3h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 44.7%, and the selectivity of PX is 43.8%.
Embodiment 5.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature23MPa, then heats to 280 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 63.8%, and the selectivity of PX is 31.0%.
Embodiment 6.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature23MPa, then heats to 350 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 100%, and the selectivity of PX is 90.1%.
Embodiment 7.
0.1gPET is joined in 50mL autoclave, add 0.001gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature27MPa, then heats to 280 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 73.6%, and the selectivity of PX is 20.7%.
Embodiment 8.
0.1gPET is joined in 50mL autoclave, add 0.02gRuSnPd catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 280 DEG C, reacts 5h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 100%, and the selectivity of PX is 82.1%.
Embodiment 9.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 300 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 100%, and the selectivity of PX is 91.0%.
Embodiment 10.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 280 DEG C, reacts 13h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 100%, and the selectivity of PX is 77.0%.
Embodiment 11.
0.1gPET is joined in 50mL autoclave, add 0.01gRuSnPt catalyst, use N2Air in displacement autoclave, iterative cycles 3 times, it is filled with H under room temperature25MPa, then heats to 260 DEG C, reacts 7h.Reaction post analysis calculates it can be seen that the degradation rate of PET is 68.6%, and the selectivity of PX is 42.3%.
Claims (9)
1. the method being prepared xylol by waste PET hydrogenation degraded, it is characterized in that: catalyst is placed in autoclave with PET by certain mass ratio, it is filled with hydrogen under room temperature, a period of time is reacted after being heated to reaction temperature, reaction uses solvent clean autoclave after terminating, removing undecomposed PET and catalyst, product, through separating and purification, obtains xylol.
2. the method according to right 1, it is characterised in that the catalyst adopted is RuSnX catalyst, wherein X is the 3rd component.
3. the method according to right 2, it is characterised in that described 3rd component is the one in Pt, Pd, Co, Ni or Rh.
4. the method according to right 1, it is characterised in that this reaction can carry out in one or several the mixture in hexamethylene, normal hexane, dioxane, oxolane.
5. the method according to right 1, it is characterised in that this reaction carries out under condition of no solvent.
6. the method according to right 1, it is characterised in that catalyst and PET mass ratio are 1%～20%.
7. the method according to right 1, it is characterised in that the Hydrogen Vapor Pressure being filled with under room temperature is 3～7MPa, reaction temperature is 240～350 DEG C, and the response time is 3～13h.
8. the method according to right 1, it is characterised in that the Hydrogen Vapor Pressure being filled with under room temperature is preferably 4～6MPa, and reaction temperature is preferably 280～320 DEG C, and the response time is preferably 7～11h.
9. the method according to right 1, it is characterised in that reaction is one or several the mixture in methanol, ethanol, acetone, ether for cleaning the solvent of autoclave after terminating.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007596A (en) * | 1998-06-22 | 2000-01-11 | Mitsubishi Chemicals Corp | Production of 1,4-cyclohexanedimethanol |
| CN105294393A (en) * | 2015-11-05 | 2016-02-03 | 中国科学院过程工程研究所 | Method for preparing 1,4-cyclohexanedimethanol through one-pot hydrogenation |
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- 2016-04-05 CN CN201610205768.1A patent/CN105712833B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007596A (en) * | 1998-06-22 | 2000-01-11 | Mitsubishi Chemicals Corp | Production of 1,4-cyclohexanedimethanol |
| CN105294393A (en) * | 2015-11-05 | 2016-02-03 | 中国科学院过程工程研究所 | Method for preparing 1,4-cyclohexanedimethanol through one-pot hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| MAKOTO TOBA等: "Synthesis of alcohols and diols by hydrogenation of carboxylic acids and esters over Ru–Sn–Al2O3 catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
| SHIN-ICHI TANIGUCHI等: "Effect of Pt addition to Ru–Sn/Al2O3 catalyst on hydrogenation of methyl laurate", 《APPLIED CATALYSIS A: GENERAL》 * |
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