CN105348557B - A kind of method of polyethylene degradation, product and application - Google Patents
A kind of method of polyethylene degradation, product and application Download PDFInfo
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- CN105348557B CN105348557B CN201410415203.7A CN201410415203A CN105348557B CN 105348557 B CN105348557 B CN 105348557B CN 201410415203 A CN201410415203 A CN 201410415203A CN 105348557 B CN105348557 B CN 105348557B
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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
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Abstract
The invention discloses a kind of method of polyethylene degradation, product and applications.The present invention provides a kind of methods of polyethylene degradation, include the following steps：Under the conditions of existing for the alkane dehydrogenating catalyst and olefin metathesis catalyst, by C2~C10Alkane and polyethylene cross over many times metathesis reaction, obtain the product of polyethylene degradation；Alkane dehydrogenating catalyst such as Formula X-R(PCP)IrL、X‑R(POCOP) shown in IrL or heterogeneous alkane dehydrogenating catalyst, olefin metathesis catalyst is the rheium oxide of gama-alumina load, Schrock type catalyst, the mixture of the cobalt oxide and molybdenum oxide of silicon dioxide carried tungstic acid or gama-alumina load.It is liquid fuel or polyvinyl paraffin wax that the present invention, which realizes polyethylene degradation, and reaction condition is mild, overcomes the disadvantages such as traditional polyethylene degradation method reaction temperature is high, product is complicated, product application value is low, has good industrial prospect.
Description
Technical field
The present invention relates to a kind of method of polyethylene degradation, product and applications.
Background technique
Plastics are important organic synthesis high molecular material, very widely used in daily life.Most of waste and old modelings
Material is to be handled by way of burning, but the process can release toxic gas and carbon dioxide, cause damages to environment.One is small
Part waste plastic recycles, and is converted into low quality plastics.Polyethylene is common plastics variety, and annual output is more than 100,000,000
Ton.Its medium high density polyethylene (HDPE) and low density polyethylene (LDPE) (LDPE) account for about the 40% of municipal solid wastes
(J.Anal.Appl.Pyro.2009,86,293-303).Polyethylene and polypropylene relative to polyethylene terephthalate and
For polystyrene, the recycling of raw material is more difficult.Wherein, the quaternary carbon of each segment is oxidized easily in polypropylene, can be with
It is degraded by heating or ultraviolet irradiation mode.And polyethylene is difficult to degrade with respect to relatively inert without specially treated.
High temperature pyrolysis (>400 DEG C) it is similar to crude oil pyrolysis, it is applied to polyethylene degradation.However, that there are efficiencies is low for this method
The disadvantages of complicated with product.Currently, have the method for many report silicon load Lewis acid catalyst catalyzed polyethylene degradations, still,
Such methods reaction temperature it is higher (>400 DEG C), selectivity of product is poor, can generate aliphatic and aromatic compound (ACS
Cata.2012,2,1924-1941；Chem.Commun.1998,1975-1976).1998, Dufaud and Basset were reported
The Ziegler-Natta catalyst of the silicon load of strong electrophilicity carries out hydrogenolysis to polyethylene and polypropylene and hydrogen
(Angew.Chem.Int.Ed.1998,37,806-810).Although the reaction efficiently, generates the lower methane of application value
And ethane.The same year, Sen and Pifer report the degradation of polyethylene under oxidizing condition, polyethylene and nitric oxide, oxygen reaction
It is converted into short chain α, ω-bisgallic acid mixture (Angew.Chem.Int.Ed.1998,37,3306-3308).
Therefore, the product recycle value that mild condition, selectivity is good, by-product is few, reaction conversion ratio is high, produces is found
Height, polyethylene degradation method that is environmental-friendly, being suitable for industrialized production are current technical problems urgently to be solved.
Summary of the invention
The technical problems to be solved by the invention are severe in order to overcome the biodegrading process reaction condition of polyethylene in the prior art
Quarter, poor selectivity, by-product be more, reaction conversion ratio the, production product without recycle value, be not suitable for industrialized production etc.
Defect, and provide method, product and the application of a kind of polyethylene degradation.The method reaction condition of polyethylene degradation of the invention
Mildly, selectivity is good, by-product is few, reaction conversion ratio is high, the product recycle value of production is high, environmental-friendly, be suitable for work
Industry metaplasia produces.
The present invention provides a kind of methods of polyethylene degradation comprising following steps：In alkane dehydrogenating catalyst and alkene
Under the conditions of hydrocarbon metathesis catalyst is existing, by C2~C10Alkane and polyethylene cross over many times metathesis reaction
(metathesis reaction), obtains the product of polyethylene degradation；The alkane dehydrogenating catalyst such as Formula X-R
(PCP) shown in IrL, such as Formula X-R(POCOP) IrL is shown or is heterogeneous alkane dehydrogenating catalyst, the olefin metathesis
Catalyst is the rheium oxide (γ-Al of gama-alumina load2O3The Re of load2O7), Schrock type catalyst, silica is born
The tungstic acid of load, or " cobalt oxide of gama-alumina load and the mixture of molybdenum oxide ",
Wherein, R C1~C6Alkyl (such as ethyl, isopropyl or tert-butyl), C5~C12Naphthenic base (such as hexamethylene
Base), C10~C12Bridge ring alkyl (such as adamantyl), X be hydrogen, C1~C6Alkoxy (such as methoxyl group), C1~C6Alkane
Base amino (such as methylamino, ethylamino, the third amino, isopropylamino or tert-butylamine base), OM orM is alkali metal (example
Such as potassium atom), R1For C1~C6Alkyl (such as ethyl, isopropyl or tert-butyl)；A and B is each independently CH or nitrogen is former
Son；L is C2H4、H2、H4Or " H2And H4Mixture "；"H2/H4" indicate H2、H4Or " H2And H4Mixture ".
In the present invention, the alkane dehydrogenating catalyst X-R(PCP) IrL preferred catalyst 1；The dehydrating alkanes are urged
Agent X-R(POCOP) IrL preferred catalyst 2, catalyst 3, catalyst 4 or catalyst 5, further preferred catalyst 2 or catalysis
Agent 4, still further preferably catalyst 2；
In the present invention, the heterogeneous alkane dehydrogenating catalyst can be normal in alkane catalytic dehydrogenating reaction in this field
Rule heterogeneous alkane dehydrogenating catalyst, such as alumina load platinum catalyst, carbon load platinum catalyst or carbon load
Palladium catalyst.
In the present invention, " multiple " is preferably 2 times to " degradation rate of polyethylene be greater than 90% number ".Described
" degradation rate of polyethylene " can be using the traditional test methods monitoring in this field, and the polyethylene residual volume separated is aobvious
Show.
In the present invention, the preferred polyvinyl paraffin wax of the product of the polyethylene degradation or liquid fuel, further preferred bavin
Oil；" liquid fuel " refers to C8~C40The mixture of short chain alkanes composition." polyvinyl paraffin wax " can also be into
One step is degraded to liquid fuel.The diesel oil refers to C9~C19The mixture of short chain alkanes composition.
In the present invention, the polyethylene refers to that polyethylene conventional in the art, molecular weight are 500~3 × 106。
The polyethylene can be linear low density polyethylene (LLDPE), low density polyethylene (LDPE) (LDPE) or high density polyethylene (HDPE)
(HDPE)。
In the present invention, the C2~C10The preferred C of alkane5~C8Alkane, further preferred n-hexane, normal heptane, just
One of octane and petroleum ether are a variety of.
In the present invention, the cross-metathesis can be in C2~C10Alkane both made reactant or done reaction dissolvent
Under conditions of carry out, can also remove " the C2~C10Alkane " other than other solvents it is existing under the conditions of carry out.When
When carrying out under the conditions of the cross-metathesis is existing for other solvents, " other solvents " can be aromatic hydrocarbons
Solvent, the aromatic hydrocarbon solvent can be toluene.
In the present invention, the C2~C10Alkane and the polyethylene weight ratio preferably 5:1~100:1, into one
Step preferably 10:1~40:1.
In the present invention, the weight ratio preferably 1 of the alkane dehydrogenating catalyst and the polyethylene:100~1:3, into
One step preferably 1:30~1:50.
The weight percent 2%~10% of rheium oxide in heretofore described " rheium oxide of gama-alumina load ", into
One step preferably 5%~10%, the weight percent refer to that the weight of rheium oxide accounts for rheium oxide and gama-alumina total weight
Percentage.
In the present invention, the weight percent preferably 2% of tungstic acid in " the silicon dioxide carried tungstic acid "
~15%, further preferred 8%~15%, the weight percent refers to that the weight of tungstic acid accounts for silica and three oxygen
Change the percentage of tungsten total weight.
In the present invention, cobalt oxide weight percent in " cobalt oxide of alumina load and the mixture of molybdenum oxide "
It is preferred that 2%~10%, further preferred 3.5%~10%, the weight percent refer to the weight of cobalt oxide account for aluminium oxide,
The percentage of cobalt oxide and molybdenum trioxide total weight.Three in " cobalt oxide of alumina load and the mixture of molybdenum oxide "
Molybdenum oxide weight percent preferably 5%~20%, further preferred 14%~20%, the weight percent refers to three oxidations
The weight of molybdenum accounts for the percentage of aluminium oxide, cobalt oxide and molybdenum trioxide total weight.
In the present invention, the Schrock type catalyst refers to that central metal is the olefin metathesis catalyst of molybdenum.
In the present invention, the weight ratio preferably 1 of the olefin metathesis catalyst and the polyethylene:1~1：20, into
One step preferably 1:3~1:10.
In the present invention, the cross-metathesis can use cross-metathesis temperature conventional in the art
It spends, particularly preferred 100 DEG C~300 DEG C in the present invention, further preferred 100 DEG C~200 DEG C, still further preferably 150 DEG C~175
℃。
In the present invention, it is the end reacted that the cross-metathesis, which is preferably greater than 90% with the degradation rate of polyethylene,
Point, the reaction time preferably 48 hours~148 hours." degradation rate of polyethylene " can be using the conventional survey in this field
Method for testing monitoring, the polyethylene residual volume separated are shown.
In the present invention, C is can be used in the polyethylene degradation method2~C10Alkane be both used as reaction substrate or done
Solvent, under alkane dehydrogenating catalyst and olefin metathesis catalyst collective effect, C2~C10Alkane and polyethylene occur alkane
Hydrocarbon double decomposition.Because of C2~C10Alkane largely exist with respect to polyethylene, so C2~C10Alkane and polyethylene occur the
The product of cross metathesis has great probability and C2~C10Second of cross metathesis of alkane further progress.Pass through
Multiple and C2~C10Alkane carry out cross metathesis, polyethylene can be converted to liquid fuel or polyethylene wax.Described
The schematic diagram of cross-metathesis is as shown in Figure 1.
In the present invention, the polyethylene degradation method, it is preferred to use following steps：
The present invention also provides the products of polyethylene degradation made from the method for the polyethylene degradation.The poly- second
The preferred polyvinyl paraffin wax of product or liquid fuel of alkene degradation, further preferred diesel oil；" liquid fuel " refers to C8~
C40The mixture of short chain alkanes composition." polyvinyl paraffin wax " can also further be degraded to liquid fuel.The bavin
Oil refers to C9~C19The mixture of short chain alkanes composition.
Application the present invention also provides the product of the polyethylene degradation as liquid fuel or polyvinyl paraffin wax.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：It is liquid fuel or polyethylene stone that the present invention, which realizes polyethylene degradation,
Wax overcomes the disadvantages such as reaction temperature existing for traditional polyethylene degradation method is high, product is complicated, product application value is low.This
The polyethylene degradation method of invention is to occur to intersect alkane metathesis using or mixtures thereof low-carbon alkanes and polyethylene, is realized poly-
Ethylene carbon chain break is gradually degraded as liquid fuel or ethylene paraffin.This method can will be without specially treated polyethylene
Domestic refuse (including the additives such as plasticizer, antioxidant, lubricant, stabilizer) high density polyethylene (HDPE), low density polyethylene (LDPE)
It is degraded to liquid fuel or polyvinyl paraffin wax.This method polyethylene degradation product is aliphatic alkane, and reaction condition is mild, has
Good industrial prospect.
Detailed description of the invention
Fig. 1 is the schematic diagram of cross-metathesis；M is 0-4；X is 0-4；Y is 0-4；Indicate Polyethylene Chain.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Catalyst 1 used in embodiment is reference literature Chem.Commun., the preparation of method described in 1996,2083 and
?.Catalyst 2,3,4,5 used in embodiment is reference literature Adv.Synth.Catal., side described in 2010,352,125
Method is prepared.The rheium oxide that the gama-alumina that olefin metathesis catalyst weight ratio used in embodiment is 5% loads
(5wt%Re2O7/γ-Al2O3) be reference literature Adv.Synth.Catal., the preparation of method described in 2010,352,125 and
?.The polyethylene that Mw is 3300 is prepared according to the method that patent 201110008851.7 is reported.Solvable production in the present invention
The total concentration of product is measured by GC, specific formula for calculation is as follows using mesitylene as internal standard：
C (total concentrations of soluble products)=∑ Ai×Ii×nm/(V×Am)
Wherein, AiFor the GC peak area A for the alkane that carbon atom number is imFor the peak area of internal standard mesitylene, IiFor carbon original
Subnumber is correction factor of the alkane with respect to mesitylene of i, nmFor the amount of the substance of addition internal standard mesitylene, V is total volume.
Embodiment 1-8:The screening of alkane dehydrogenating catalyst in polyethylene degradation reaction
Every group of reaction is two control reactions, one of them is added without polyethylene, and 120mg polyethylene is added in another.
In argon gas glove box, 20 μm of ol alkane dehydrogenating catalysts of addition in the Schlenk bottle dry to 10mL (1,2,3,
4 or 5), 3.0mL n-hexane, stirring dissolves catalyst.Add 506mg γ-Al2O3, stir about 15min, make catalyst into
Row load.Then rheium oxide (the 5wt%Re that the gama-alumina that 546mg weight percent is 5% loads is added2O7/γ-
Al2O3), 20 μ L mesitylene are internal standard.One of them in every group of experiment adds 120mg polyethylene (Mw=3350, Mn=
2080, PDI=1.6), another is added without polyethylene, is blank control.It is sealed with the cock of polytetrafluoroethylene (PTFE), 150 DEG C of oil
Bath heating 3 days.After heating, supernatant GC is taken to monitor, calculates turn over number.Residue is filtered while hot with normal octane, will be remaining
Polyethylene filter out, separation drain weighing.Specific data are shown in Table 1.1. γ-Al of table2O3The iridium catalyst (20 μm of ol) of load
Rheium oxide (the 5wt%Re that the gama-alumina for being 5% with weight percent loads2O7/γ-Al2O3) catalysis HDPE-1 (120mg)
With the intersection alkane metathesis of n-hexane (3.0mL)：The conversion ratio of the distributions of alkane products and polyethylene to fuel
Table 1
Conversion ratio=1- (polyethylene residual volume/polyethylene additional amount)
Embodiment 9-20:The degradation reaction of different polyethylene
In argon gas glove box, 4.2 μm of ol alkane dehydrogenating catalysts of addition in the Schlenk bottle dry to 10mL (4 or
2), normal octane (2.5mL or 4.0mL), stirring dissolve catalyst.Add the gamma oxidation that 546mg weight percent is 5%
Rheium oxide (the 5wt%Re of aluminium load2O7/γ-Al2O3), stir about 15min loads catalyst.Then 20 μ L are added
Mesitylene is internal standard.Be eventually adding polyethylene, be then sealed with the cock of polytetrafluoroethylene (PTFE), 175 DEG C oil bath heating 4 days.
After heating, supernatant GC is taken to monitor, calculates turn over number.Residue is filtered while hot with normal octane, by remaining polyethylene mistake
It filters out and, weighing is drained in separation, and surveys molecular weight with GPC.
Rheium oxide (the 5wt%Re that the gama-alumina that table 2.Ir (4.2 μm of ol) and weight percent are 5% loads2O7/γ-
Al2O3) it is catalyzed the degradation of different polyethylene and normal octane (2.5 or 4.0mL)：The distributions of alkane products and polyethylene are to fuel
Conversion ratio
Embodiment 21:Polyethylene and petroleum ether Degradation and Transformation are the reaction of fuel
In argon gas glove box, 4.2 μm of ol alkane dehydrogenating catalysts 2, petroleum is added in the Schlenk bottle dry to 15mL
Ether (bp.35-60 DEG C, 8.0mL), stirring dissolve catalyst.It is negative to add the gama-alumina that 819mg weight percent is 5%
Rheium oxide (the 5wt%Re of load2O7/γ-Al2O3), stir about 15min loads catalyst.It is eventually adding articles for daily use
Vinyon box (306mg), is then sealed with the cock of polytetrafluoroethylene (PTFE), 175 DEG C oil bath heating 4 days.After heating,
Petroleum ether filtering, the alkane for being dissolved in petroleum ether is washed out, and volatile matter is removed in filtrate concentration.Obtain 0.41g fuel.
It is it is necessary to described herein finally：Above-described embodiment is served only for making technical solution of the present invention further detailed
Ground explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention
The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.
Claims (16)
1. a kind of method of polyethylene degradation, it is characterised in that it includes the following steps：It is multiple in alkane dehydrogenating catalyst and alkene
Under the conditions of decomposition catalyst is existing, by C2~C10Alkane and polyethylene cross over many times metathesis reaction, obtain poly- second
The product of alkene degradation；The alkane dehydrogenating catalyst such as Formula X-R(PCP) shown in IrL, such as Formula X-R(POCOP) IrL institute
Show or for heterogeneous alkane dehydrogenating catalyst, the olefin metathesis catalyst be the rheium oxide of gama-alumina load,
Schrock type catalyst, silicon dioxide carried tungstic acid, or " cobalt oxide of gama-alumina load and mixing for molybdenum oxide
Close object ",
Wherein, R C1~C6Alkyl, C5~C12Naphthenic base, C10~C12Bridge ring alkyl, X be hydrogen, C1~C6Alkoxy,
C1~C6Alkyl amino, OM orM is alkali metal, R1For C1~C6Alkyl；A and B is each independently CH or nitrogen
Atom；L is C2H4、H2、H4Or " H2And H4Mixture ".
2. the method for polyethylene degradation as described in claim 1, it is characterised in that：
When the R is C1~C6Alkyl when, " the C1~C6Alkyl " be ethyl, isopropyl or tert-butyl；
And/or
When the R is C5~C12Naphthenic base when, " the C5~C12Naphthenic base " be cyclohexyl；
And/or
When the R is C10~C12Bridge ring alkyl when, " the C10~C12Bridge ring alkyl " be adamantyl；
And/or
When the X is C1~C6Alkoxy when, " the C1~C6Alkoxy " be methoxyl group；
And/or
When the X is C1~C6Alkyl amino when, " the C1~C6Alkyl amino " be methylamino, ethylamino, the third ammonia
Base, isopropylamino or tert-butylamine base；
And/or
When the M is alkali metal, " alkali metal " is potassium atom；
And/or
As the R1For C1~C6Alkyl when, " the C1~C6Alkyl " be ethyl, isopropyl or tert-butyl.
3. the method for polyethylene degradation as described in claim 1, it is characterised in that：
The heterogeneous alkane dehydrogenating catalyst is the platinum catalyst of alumina load, the platinum catalyst of carbon load or carbon load
Palladium catalyst；
And/or
The alkane dehydrogenating catalyst X-R(PCP) IrL is catalyst 1；
And/or
The alkane dehydrogenating catalyst X-R(POCOP) IrL be catalyst 2, catalyst 3, catalyst 4 or catalyst 5,
And/or
It is described it is " multiple " be 2 times to " degradation rate of polyethylene is greater than 90% number ".
4. the method for polyethylene degradation as described in claim 1, it is characterised in that：The product of the polyethylene degradation is poly-
Ethylene paraffin or liquid fuel.
5. the method for polyethylene degradation as claimed in claim 4, it is characterised in that：" liquid fuel " refers to C8~C40
The mixture of short chain alkanes composition.
6. the method for polyethylene degradation as claimed in claim 4, it is characterised in that：The liquid fuel is diesel oil, described
Diesel oil refer to C9~C19The mixture of short chain alkanes composition.
7. the method for polyethylene degradation as described in claim 1, it is characterised in that：
Its molecular weight of the polyethylene is 500~3 × 106；
And/or
The polyethylene is linear low density polyethylene, low density polyethylene (LDPE) or high density polyethylene (HDPE)；
And/or
The C2~C10Alkane be C5~C8Alkane；
And/or
The alkane dehydrogenating catalyst is catalyst 2 or catalyst 4；
And/or
The weight percent of rheium oxide is 2%~10% in " rheium oxide of gama-alumina load ", the weight hundred
Ratio is divided to refer to that the weight of rheium oxide accounts for the percentage of rheium oxide and gama-alumina total weight；
And/or
The weight percent of tungstic acid is 2%~15% in " the silicon dioxide carried tungstic acid ", the weight
Amount percentage refers to that the weight of tungstic acid accounts for the percentage of silica and tungstic acid total weight；
And/or
Cobalt oxide weight percent is 2%~10% in " cobalt oxide of alumina load and the mixture of molybdenum oxide ",
The weight percent refers to that the weight of cobalt oxide accounts for the percentage of aluminium oxide, cobalt oxide and molybdenum trioxide total weight；It is described
" cobalt oxide of alumina load and the mixture of molybdenum oxide " in molybdenum trioxide weight percent be 5%~20%, it is described
Weight percent refers to that the weight of molybdenum trioxide accounts for the percentage of aluminium oxide, cobalt oxide and molybdenum trioxide total weight；
And/or
The Schrock type catalyst refers to that central metal is the olefin metathesis catalyst of molybdenum.
8. the method for polyethylene degradation as claimed in claim 7, it is characterised in that：
The weight percent of rheium oxide is 5%~10% in " rheium oxide of gama-alumina load ", the weight hundred
Ratio is divided to refer to that the weight of rheium oxide accounts for the percentage of rheium oxide and gama-alumina total weight；
And/or
The weight percent of tungstic acid is 8%~15% in " the silicon dioxide carried tungstic acid ", the weight
Amount percentage refers to that the weight of tungstic acid accounts for the percentage of silica and tungstic acid total weight；
And/or
In " cobalt oxide of alumina load and the mixture of molybdenum oxide " cobalt oxide weight percent be 3.5%~
10%, the weight percent refers to that the weight of cobalt oxide accounts for the percentage of aluminium oxide, cobalt oxide and molybdenum trioxide total weight；
Molybdenum trioxide weight percent is 14%~20% in " cobalt oxide of alumina load and the mixture of molybdenum oxide ", institute
The weight percent stated refers to that the weight of molybdenum trioxide accounts for the percentage of aluminium oxide, cobalt oxide and molybdenum trioxide total weight；
And/or
The C5~C8Alkane be one of n-hexane, normal heptane, normal octane and petroleum ether or a variety of；
And/or
The alkane dehydrogenating catalyst is catalyst 2.
9. the method for polyethylene degradation as described in claim 1, it is characterised in that：
The cross-metathesis is in C2~C10Alkane both made reactant or done to carry out under conditions of reaction dissolvent, or
Person is removing the " C2~C10Other outer solvents of alkane " it is existing under the conditions of carry out；
And/or
The C2~C10Alkane and the weight ratio of the polyethylene be 5:1~100:1；
And/or
The weight ratio of the alkane dehydrogenating catalyst and the polyethylene is 1:100~1:3；
And/or
The weight ratio of the olefin metathesis catalyst and the polyethylene is 1:1~1：20；
And/or
The temperature of the cross-metathesis is 100 DEG C~300 DEG C；
And/or
It is the terminal reacted that the cross-metathesis, which is greater than 90% with the degradation rate of polyethylene,.
10. the method for polyethylene degradation as claimed in claim 9, it is characterised in that：
When carrying out under the conditions of the cross-metathesis is existing for other solvents, " other solvents " is aromatic hydrocarbons
Class solvent；
And/or
The C2~C10Alkane and the weight ratio of the polyethylene be 10:1~40:1；
And/or
The weight ratio of the alkane dehydrogenating catalyst and the polyethylene is 1:30~1:50；
And/or
The weight ratio of the olefin metathesis catalyst and the polyethylene is 1:3~1：10；
And/or
The temperature of the cross-metathesis is 100 DEG C~200 DEG C；
And/or
The time of the cross-metathesis is 48 hours~148 hours.
11. the method for polyethylene degradation as claimed in claim 10, it is characterised in that：The temperature of the cross-metathesis
Degree is 150 DEG C~175 DEG C.
12. the product of polyethylene degradation made from the method for polyethylene degradation as claimed in any one of claims 1 to 11.
13. the product of polyethylene degradation as claimed in claim 12, it is characterised in that：The product of the polyethylene degradation is
Polyvinyl paraffin wax or liquid fuel.
14. the product of polyethylene degradation as claimed in claim 13, it is characterised in that：" liquid fuel " refers to C8~
C40The mixture of short chain alkanes composition.
15. the product of polyethylene degradation as claimed in claim 13, it is characterised in that：The liquid fuel is diesel oil, institute
The diesel oil stated refers to C9~C19The mixture of short chain alkanes composition.
16. application of the product of polyethylene degradation as claimed in claim 13 as liquid fuel or polyvinyl paraffin wax.
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| WO2022090506A1 (en) * | 2020-10-30 | 2022-05-05 | Basell Poliolefine Italia S.R.L. | Supported metal oxides as depolymerization catalysts |
| WO2023245043A1 (en) * | 2022-06-17 | 2023-12-21 | Dow Global Technologies Llc | Processes for converting saturated polyethylene to alkene products |
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| CN112625341A (en) * | 2020-12-07 | 2021-04-09 | 上海大学 | Degradable and recyclable melt-blown material and preparation method thereof |
| CN115703900B (en) * | 2021-08-09 | 2024-07-05 | 复旦大学 | Photocatalytic degradation method of polyolefin |
| WO2023245045A1 (en) * | 2022-06-17 | 2023-12-21 | Dow Global Technologies Llc | Processes for converting unsaturated polyethylene to alkene products |
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| CN101253132A (en) * | 2005-07-08 | 2008-08-27 | 北卡罗来纳-查佩尔山大学 | A dual catalyst system for alkane metathesis |
| CN101885857A (en) * | 2010-07-14 | 2010-11-17 | 宁波卡利特新材料有限公司 | Simple method for preparing polyethylene wax from waste plastic |
| CN102424710A (en) * | 2011-11-25 | 2012-04-25 | 四川大学 | Method for preparing chain-end chlorinated polyethylene wax through thermal degradation of copper chloride |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101253132A (en) * | 2005-07-08 | 2008-08-27 | 北卡罗来纳-查佩尔山大学 | A dual catalyst system for alkane metathesis |
| CN101885857A (en) * | 2010-07-14 | 2010-11-17 | 宁波卡利特新材料有限公司 | Simple method for preparing polyethylene wax from waste plastic |
| CN102424710A (en) * | 2011-11-25 | 2012-04-25 | 四川大学 | Method for preparing chain-end chlorinated polyethylene wax through thermal degradation of copper chloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022090506A1 (en) * | 2020-10-30 | 2022-05-05 | Basell Poliolefine Italia S.R.L. | Supported metal oxides as depolymerization catalysts |
| WO2023245043A1 (en) * | 2022-06-17 | 2023-12-21 | Dow Global Technologies Llc | Processes for converting saturated polyethylene to alkene products |
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| CN105348557A (en) | 2016-02-24 |
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