CN108456354A - Polymer matches mixing composition and its recycling method - Google Patents

Polymer matches mixing composition and its recycling method Download PDF

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Publication number
CN108456354A
CN108456354A CN201810158580.5A CN201810158580A CN108456354A CN 108456354 A CN108456354 A CN 108456354A CN 201810158580 A CN201810158580 A CN 201810158580A CN 108456354 A CN108456354 A CN 108456354A
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CN
China
Prior art keywords
polymer mixture
polymer
mixture according
plastic product
clay
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Pending
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CN201810158580.5A
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Chinese (zh)
Inventor
沃努·丹他帕尼查库恩
帕查拉卡莫·菲斯安特库
苏查特·蓬查佛
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Grd Innovation Ltd
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Grd Innovation Ltd
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Publication of CN108456354A publication Critical patent/CN108456354A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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

Abstract

The present invention relates to polymer to match mixing composition and plastics recycling method, the composition includes a part of polymer and a part of Cracking catalyst being compounded therewith, the method is for cycling and reutilization plastic product made of the polymer mixture of the present invention, wherein can get Light hydrocarbon products.

Description

Polymer matches mixing composition and its recycling method
Technical field
The present invention relates to polymer to match mixing composition, the application of polymer mixture and plastics recycling method.
Background technology
Due to the numerous characteristics of plastics, including lighter weight, intensity, durability, formability, toughness and more just Suitable cost has been widely used for replacing some other material.The increased major consequences of plastics consumption are plastics after consumption The accumulation of waste, this may need centuries that could decompose.
Landfill is one of processing most common alternative approach of plastic wastes.However, which results in chemical contamination soil And water.
Cycling and reutilization plastic wastes have caused very as a kind of alternative of more environmentally friendly plastic wastes processing More concerns.It is simple mechanically to carry out method required when cycling and reutilization, but the regenerated plastics obtained are usually with relatively low Physical property.On the other hand, cycling and reutilization is chemically carried out to has the following advantages：Recycle polymer chemistry at Point, it can be used for remanufacturing plastics later or prepare other synthesis of chemicals.
In the case of no catalyst, chemically cycling and reutilization plastics may carry out at high temperature, temperature Generally 800-1,000 DEG C or higher.In addition, there are suitable catalyst, can at much lower temperature into The cycling and reutilization of row chemical mode.
Chinese patent application disclose CN101168678A disclose it is a kind of using contain the phosphate-modified zeolites of KDC-1 and height The method that the catalyst of ridge soil carrys out cycling and reutilization plastic wastes (especially polyethylene and polypropylene), wherein primary product is to split Solution oil and diesel oil.
United States Patent (USP) US7,932,424B2 disclose a kind of method for catalytic cracking waste plastics, wherein solid is given up Plastics are loaded into the horizontal reacting container including orbiting vane blender, and inner containment has graininess FCC dead catalyst With the mixture of graininess Ca compounds, which is heated to 350-435 DEG C of temperature range, wherein FCC dead catalyst Amount be eaction vessel capacity 20-60 volume %, and Ca compounds are to be 15- relative to 100 mass parts FCC dead catalyst The amount of 50 mass parts exists.The selectivity for the oil distillate product that this method provides improved within the scope of C5-C10.
United States Patent (USP) US8,344,195B2 disclose a kind of method producing fuel by plastic waste comprising by plastics Waste pyrolysis generates fluent material, then in the reactor mixes the fluent material with dolomite catalysts and is split with carrying out catalysis Change.
The purpose of the present invention is by providing a kind of polymer mixture and its application and a kind of cycling and reutilization, this is poly- The method for closing object mixing material, to overcome the deficiencies of existing technologies, wherein the method and uncomplicated, and reach for light hydrocarbon Product it is highly selective.
Invention content
The purpose of the present invention is achieved by providing following polymer mixture, and the polymer mixture includes：
(a) polymer of 50-99 weight %；With
(b) Cracking catalyst of 1-50 weight %.
In addition, the purpose of the present invention is achieved by providing following plastics recycling method, the method packet It includes：The plastic product made of Inventive polymers mixing material is heated to the temperature within the scope of 200-1,000 DEG C.
Specific implementation mode
The present invention relates to a kind of polymer mixture, it includes：(a) polymer of 50-99 weight %；(b) 1-50 weights Measure the Cracking catalyst of %.
The term as used herein " polymer " refers to very big containing being made of a series of small basic units (monomer) Molecule material.It can be homopolymer, can also be copolymer.
In one embodiment, the polymer is selected from polyethylene, polypropylene, polystyrene, poly terephthalic acid second Diol ester, polyvinyl chloride, polymethyl methacrylate and their arbitrary combination.
In preferred embodiments, the polymer is selected from polyethylene, polypropylene and combination thereof, more preferably For polyethylene.
In other preferred embodiment, the polymer is selected from low density polyethylene (LDPE) (LDPE), linea low density Polyethylene in polyethylene (LLDPE), medium density polyethylene and high density polyethylene (HDPE) (HDPE), more preferably high-density polyethylene Alkene.
The term as used herein " high density polyethylene (HDPE) " or " HDPE " refer to mass density in 0.93-0.97g/cm3Range Interior polyethylene.
In the another embodiment of the present invention, the polymer is mass density in 0.93-0.96g/cm3In range High density polyethylene (HDPE).
In a further embodiment of the invention, the polymer is melt flow index in 0.04-18g/10min (190 DEG C, 2.6kg) high density polyethylene (HDPE) in range.
Melt flow index used herein or MFI refer to weighing melt of thermoplastic polymers flowing complexity Amount.It is defined as：Polymer under defined backup temperature, under the counterweight pressure applied of defined alternative weight, The quality grams of the capillary with special diameter and length is flowed through in ten minutes.This method is in similar standard ASTM It is described in D1238 and ISO 1133.
Preferably, the polymer mixture includes the polymer of 70-99 weight %, more preferable 80-99 weight %'s Polymer.
The term as used herein " Cracking catalyst " refers to any cracking catalysis material that can be used for making hydrocarbon cracking.
In one embodiment, the Cracking catalyst is porous acid solid material.The porous acid solid material It is double that material is preferably selected from acid clay, aluminium oxide, silica, zeolite, zirconium oxide, zinc oxide, titanium dioxide, magnesia, stratiform Oxide (layered double oxide) and their arbitrary combination, more preferably acid clay.
Acid clay can be obtained naturally.The acid clay is preferably nonacid viscous by being handled with acidic chemical Native (more preferable POLARGEL NF) is prepared.
The term as used herein " bentonite " refers to a kind of clay being substantially made of montmorillonite.Have different types of swollen Profit soil, is named with respective essential element, such as potassium bentonite, sodium bentonite, calcium bentonite and aluminium bentonite respectively.
It may further be preferable that described handle nonacid clay in the following manner to carry out with acidic chemical：With acid Property chemical solutions to nonacid clay (more preferable POLARGEL NF) carry out dipping or ion exchange.For example, acidic chemical HCl, HI, HBr, H can be selected from2SO4、(NH4)2SO4、CH3COOH、BF3、HNO3And HClO4。
Advantageously, the proton content of acid clay is at least 1 micromoles per gram.
Preferably, determine that the measurement method of material proton content can refer to document：D.E.Lopez,J.G.Goodwin Jr.,D.A.Bruce,Journal of Catalysis,245(2007)381-391。
Alternative to be, acid clay is iron-containing clay, preferably iron-containing POLARGEL NF.
Polymer mixture according to the present invention preferably comprises the Cracking catalyst of 1-30 weight %, more preferable 1-20 weights Measure the Cracking catalyst of %.
In a further embodiment, the average diameter of Cracking catalyst is in the range of 1-500 microns, preferably 100- 300 microns.
Average diameter used herein can refer to primary particle size or aggregate particle size, wherein the aggregate particle size is one to reunite The size of secondary particle.
In a further embodiment, polymer mixture, which also includes required depending on desired final use, has Help change the chemistry of polymer mixture and/or any additive and/or filler of physical property.For example, polymer is compounded Material can also include for example white material TiO2Coloring pigment.
In one embodiment, it is preferred to by by the cracking catalysis of the polymer of 50-99 weight % and 1-50 weight % Agent compounding prepares polymer mixture.
The term as used herein " compounding " refers to a kind of method producing polymer mixture comprising：By that will polymerize Object and other compositions are mixed and/or are blended in the molten state to prepare plastics formulation.
Any technology for polymer compounding known to those skilled in the art is used equally for the present invention, and unrestricted System.In one embodiment, the compounding of polymer and Cracking catalyst is carried out by extruding technology.
The term as used herein " extrusion " refers to such a method, wherein by heat or half cold soft solid material (example Such as plastics) aperture of mold is forced through to generate the continuously shaped part of required product shape.
For the present invention advantageously, being squeezed out using double screw extruder.The operating condition of extruder can be with It is widely varied according to the specification of equipment.In one embodiment, screw rod of the double screw extruder within the scope of 130-300rpm It is operated under speed.
It is also preferred that being squeezed out at a temperature of extruding machine mold within the scope of 100-230 DEG C, which is more preferably 120-210℃。
Polymer mixture according to the present invention can be used for preparing many plastic products, such as sack, bottle, film or pipe Son.
Different plastic forming methods can be carried out to polymer mixture, including is for example blow molded, is molded and rotational molding, Required plastic product is made.
In one embodiment, polymer mixture is preferably implemented by film injection method for producing plastic foil.
Preferably, implement film injection method using the double screw extruder equipped with injection film die.
It is furthermore preferred that film injection method is in 130-300rpm, more preferably 140-200rpm, further preferably 145- Implement under screw speed within the scope of 180rpm.
It is also preferred that extruding machine mold temperature of the film injection method within the scope of 100-230 DEG C, more preferably 150-210 DEG C Degree is lower to be implemented.
In addition, the purpose of the present invention is further realized by providing following plastics recycling method, it is described Method includes：(a) plastic product made of polymer mixture according to the present invention is placed in reactor；And (b) by institute State the temperature that plastic product is heated within the scope of 200-1,000 DEG C, preferably 250-800 DEG C, more preferably 350-600 DEG C.
Plastic product can be any form made of the polymer mixture of the present invention.In one embodiment, The plastic product is sack, film or combination thereof.
In a further embodiment, the plastic product is freshly prepared plastic product.
In a more preferred embodiment, the plastic product is the plastic product after consumption.
Before plastic product is placed in reactor, typically without the size for reducing plastic product, unless plastic product It cannot be fitted into reactor greatly or need to handle a greater amount of plastic products in single reactor very much.
Using the plastic product, additional catalyst need not be put into reactor.
The reactor can be any kind of.In one embodiment, the reactor is batch reactor. In alternative embodiments, the reactor be selected from fixed bed reactors, fluidized-bed reactor, moving-burden bed reactor and The flow reactor of CSTR reactors.
Reaction time needed for this method depends on a number of factors, including the amount of plastic product raw material, reactor used Type and size.
In one embodiment, the reactor is batch reactor, and to plastic product heated when Between be 0.5-10 hours, preferably 1-5 hours.
For purposes of the invention advantageously, implementing this method in an inert atmosphere.In one embodiment, this method is also Including：Before step (b) heating of plastic product, with inert gas (preferably nitrogen) purge, to be obtained in reactor Obtain substantially inert oxygen-free atmosphere.
In a further embodiment, gauge pressure is 0-10 bars, preferably gauge pressure is that implement under pressure within the scope of 1-5 bars should Method.
Inventor it was unexpectedly found that, plastics recycling method according to the present invention can use simple equipment Convert plastic product made of polymer mixture according to the present invention to light hydrocarbon, especially methane, second with high selectivity Alkane, propane and butane, they can be further used as the raw material in industrial process, or can be further purified and be used as The raw material of the synthesis of chemicals of higher value is manufactured, or it can further be distilled and as transport fuel.
Embodiment
Provide the purpose that following instance is merely to illustrate, it is not intended to limit the scope of the invention in any way.
Example 1：The preparation of Inventive polymers mixing material
It at room temperature contacts nonacid sodium bentonite clay and the ammonium sulfate of 2 weight %, is then done at 120 DEG C The dry 3 hours bentonites with production acid processing.
By MFI be 0.04g/10min (ASTM D1238) and density is 0.956g/cm3The HDPE of (ASTM D1505) is thin Powder is fully blended with the bentonite (grain size is 100 microns) of the acid processing of 7 weight %.Then the HDPE and acid are handled Bentonitic mixture be added screw speed be about 150rpm, in the double screw extruder that mold temperature is about 150 DEG C with life Produce HDPE mixing materials.
Example 2：The preparation of plastic foil of the present invention
Then, it is fed via the feeder of double screw extruder by the HDPE mixing materials for preparing example 1, HDPE is matched Batch mixing is converted to plastic foil, wherein the double screw extruder equipped with injection film die, and screw speed be 150rpm, Mold temperature is 170-220 DEG C.The yield of plastic foil is 500 grams/45 minutes.
The physical property of gained plastic foil is as shown in table 1.
Table 1
Yield tensile strength MD:217 TD:666 kg/cm2 ASTM D882
Fracture tensile strength MD:225 TD:737 kg/cm2 ASTM D882
Stretch modulus, 2% secant MD:4189 TD:3431 kg/cm2 ASTM D882
Extension at break MD:303 TD:480 kg/cm2 ASTM D882
MD=is longitudinal, and TD=is lateral
Example 3：The plastics recycling method of the present invention
The plastic foil prepared using example 2, recycling method is implemented as follows：
(1) 10 grams of plastic foils are placed in the 316 stainless steel batch reactors of 50cc.
(2) reactor is purged 5 times with nitrogen.
(3) reactor is placed in Muffle furnace and is heated to 450 DEG C, heated 2 hours, gauge pressure is 2 bars.
(4) it is cooled to the temperature less than 100 DEG C.
(5) reactor by heating is connected with GC-FID by 1/8 " stainless steel tube, to analyze product point Cloth.
Product distribution results are as shown in table 3.
Example 4：Comparative example
The step identical as described in example 1-3 is repeated, but uses nonacid sodium bentonite, and without acid processing.
Product distribution results are as shown in table 3.
Example 5：Comparative example
Described in example 2, with MFI be 0.04g/10min (ASTM D1238) and density is 0.956g/cm3(ASTM D1505 HDPE fine powders) carry out film injecting step, are not added with any Cracking catalyst.The physical property of gained plastic foil such as table 2 It is shown.
Table 2
Yield tensile strength MD:253 TD:355 kg/cm2 ASTM D882
Fracture tensile strength MD:340 TD:726 kg/cm2 ASTM D882
Stretch modulus, 2% secant MD:4347 TD:2956 kg/cm2 ASTM D882
Extension at break MD:858 TD:766 kg/cm2 ASTM D882
MD=is longitudinal, and TD=is lateral
Then, according to described in example 3, implement plastics recovery method with the plastic foil.Product distribution results are shown in table 3 In.
Example 6：Comparative example
In the 316 stainless steel batch reactors of 50cc, by 1 institute of example of plastic foil and 7 weight % described in example 5 State acid processing bentonite physical mixed, then repeatedly described in example 3 the step of (2)-(5).
Product distribution results are as shown in table 3.
Example 7：Example
The step identical as described in example 1-3 is repeated, but reactor is heated to 600 DEG C in step (3), without It is 450 DEG C.
Product distribution results are as shown in table 3.
Table 3
Example 3 Example 4 Example 5 Example 6 Example 7
Polymer HDPE HDPE HDPE HDPE HDPE
Catalyst type Acidic Bentonite Nonacid bentonite Nothing Acidic Bentonite Acidic Bentonite
Catalyst content 7% 7% 0% 7% 7%
Blend method It squeezes out It squeezes out Nothing Physical mixed in the reactor It squeezes out
Furnace temperature 450℃ 450℃ 450℃ 450℃ 600℃
Component Weight % Weight % Weight % Weight % Weight %
Methane 7.6 0.3 - - 21.6
Ethane 30.6 1.2 - 0.2 37.7
Ethylene 0.5 0.0 - - 0.5
Propane 31.0 4.3 - 0.5 24
Propylene 2.8 1.1 - - 1.4
Butane 16.0 3.3 - 1.1 9.3
Trans-2-butene 0.6 0.0 - - 0.1
1- butylene 0.4 0.0 - - 0.1
Isobutene 0.7 0.0 - - 0.1
Cis-2-butene 0.4 0.0 - 0.1 0.1
Pentane 6.5 7.6 4.3 8.3 3.3
Amylene 1.2 3.2 1.7 4.7 1
Hexane+hexene 1.7 20.2 17.6 19.1 0.8
C7+ - 58.8 76.4 66 -
It is total 100 100 100 100 100
From result above as it can be seen that being directly compounded into polymer in porous acid solid material (such as Acidic Bentonite) When, the plastic product of gained can be by conveniently and the Light hydrocarbon products that are converted into high selectivity within the scope of C1-C4.

Claims (12)

1. a kind of polymer mixture, it includes：
(a) polymer of 50-99 weight %；With
(b) Cracking catalyst of 1-50 weight %；
The wherein described Cracking catalyst is the porous acid solid material that proton content is at least 1 micromoles per gram.
2. polymer mixture according to claim 1, wherein the polymer is selected from polyethylene, polypropylene, polyphenyl second Alkene, polyethylene terephthalate, polyvinyl chloride, polymethyl methacrylate and their arbitrary combination.
3. polymer mixture according to claim 1 or 2, wherein the polymer is selected from low density polyethylene (LDPE), line Polyethylene in property low density polyethylene (LDPE), medium density polyethylene and high density polyethylene (HDPE).
4. polymer mixture according to claim 1, wherein the porous acid solid material is selected from acid clay, oxygen Change aluminium, silica, zirconium oxide, zinc oxide, titanium dioxide, magnesia, stratiform double oxide and their arbitrary combination.
5. polymer mixture according to claim 4, wherein the porous acid solid material is by with acidification Product handle acid clay prepared by nonacid clay.
6. polymer mixture according to claim 5, wherein the nonacid clay is POLARGEL NF.
7. polymer mixture according to any one of the preceding claims, wherein the average diameter of the Cracking catalyst In the range of 1-500 microns.
8. polymer mixture according to any one of the preceding claims is used to prepare the purposes of plastic product.
9. the purposes of polymer mixture according to claim 8, wherein the plastic product be sack, bottle, film or Pipe.
10. a kind of plastics recycling method comprising：
(a) plastic product made of the polymer mixture according to any one of claim 1-7 is placed in reactor In；And
(b) temperature being heated to the plastic product within the scope of 200-1,000 DEG C.
11. plastics recycling method according to claim 10, wherein the plastic product be sack, film or it Combination.
12. the plastics recycling method according to claim 10 or 11, wherein the method further include：In step (b) before, the reactor described in inert gas purge.
CN201810158580.5A 2017-02-17 2018-02-22 Polymer matches mixing composition and its recycling method Pending CN108456354A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SG10201701302Y 2017-02-17
SG10201701302YA SG10201701302YA (en) 2017-02-17 2017-02-17 Polymer Compounding Composition and Recycling Process Thereof

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Application publication date: 20180828