CN106279760A - A kind of recovery processing technique of waste polyurethane - Google Patents
A kind of recovery processing technique of waste polyurethane Download PDFInfo
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- CN106279760A CN106279760A CN201610660341.0A CN201610660341A CN106279760A CN 106279760 A CN106279760 A CN 106279760A CN 201610660341 A CN201610660341 A CN 201610660341A CN 106279760 A CN106279760 A CN 106279760A
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- polyurethane
- processing technique
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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
- 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
- C08J11/18—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 treatment with organic material
- C08J11/28—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 treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
-
- 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
- C08J11/16—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 treatment with inorganic material
-
- 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
- C08J11/18—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 treatment with organic material
- C08J11/22—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 treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—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 treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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 invention discloses the recovery processing technique of a kind of waste polyurethane, be ground into polyurethane particles including by waste polyurethane；Polyurethane particles, water, antioxidant, distintegrant and catalyst are added in reactor; and be passed through noble gas and protect; reactor is heated up in salt bath; 218 ~ 399 DEG C, keep 3 ~ 5 hours under the conditions of 50 ~ 150kPa; carbodiimide selected by catalyst, finally gives diamine, polyhydric alcohol and carbon dioxide；The steps such as separating binary amine and polyhydric alcohol.The invention has the beneficial effects as follows: by the present invention in that with carbodiimide as catalyst, product layering is promoted when can react in reactor, improve the activity of product and improve the response rate of polyurethane, make reclaim chemicals quantity many, kind is complete, and required temperature can be reduced, be conducive to saving production cost.
Description
Technical field
The present invention relates to field of waste recycle, specifically, be the recovery processing technique of a kind of waste polyurethane.
Background technology
The polymer that polyurethane (being called for short PU) is made up of raw materials such as polyisocyanates, polyhydric alcohol and cross-linking agent.Extensively should
For automobile making, refrigerator manufacture, transportation, civil construction, footwear, synthetic leather, fabric, electromechanics, petrochemical industry, mining machine
Many fields such as tool, aviation, medical treatment, agricultural.
Within 2005, global polyurethane yield breaks through 13,750,000 tons.Along with the fast development of polyurethane, its garbage the most more comes
The most.Including for a large amount of polyurethane foams of heat insulation and Sofa cushion, waste and old PU sole, waste and old PU leather etc..If
Process these waste materials, not only land occupation only by landfill and the method burned, and pollute environment, be also to resource simultaneously
A kind of waste.Therefore, the recycling problem of polyurethane be polyurethane industrial significant problem in the urgent need to address it
One, waste polyurethane is carried out recycling, reduces environmental pollution, reduce the production cost of new product simultaneously, there is reality
Meaning.
The recycling of RPUF has a following several method: physiochemical mutagens, chemical recovery and burning
Reclaim heat energy method.
Physiochemical mutagens method: then the physical aspect changing waste polyurethane foam directly utilizes, bonding extrusion forming obtains
Product.The general fine platy that is first ground into by waste polyurethane rigid foam, painting is spread polyurethane binder etc., then is passed directly into water steaming
The high-temperature gases such as gas, bonding to the waste polyurethane of powdery after making polyurethane binder melted or dissolving, then cure under pressure becomes
Definite shape.Physical can prepare construction material, insulation material, water-resistant material, filler etc..As: regenerative polyurethane foam material
Material method, main processes includes quantitatively injecting in metal pattern the mixed material stirred, foams at a certain temperature, warp
Cross the demoulding after the precuring of certain time, more i.e. can get new foam plastics through post curing.So, mixture through Over emulsfication,
Rise, gel, several stages such as solidification, old foam plastics powder is fixedly arranged among new foam plastics, forms new foam plastic
Material.This process characteristic is to manufacture dimensional standard, complex-shaped product, and loss of material is few, adds foam plastics powder the most relatively
For convenience.Polyurethane water resistant sheet material, the hard polyurethane foams waste material of refrigerator etc. is single polyurethane, many with many phenyl
Methylene polyisocyanates makees adhesive.Adhesive is dispersed between waste foam fragment, after mix homogeneously, is prefabricated into
Loose base pad, inserts in the mould scribbling releasing agent, is pressed into foam flakeboard or product under high pressure and heating.Due to firmly
Matter polyurethane waste material flakeboard has excellent water-resistance, and is commonly used to make warship marine furniture.Soft plastic material, passes through polyurethane waste material
Extrusion molding becomes strand into moderate-length chain, and PU material is transformed into soft plastic material, this material be suitable as intensity high,
Hardness is high, but working of plastics less demanding to elongation at break.For soft micropore PU foam waste, powder can be ground into
End, is blended in thermoplastic polyurethane, pelletize in extrusion shaping machine, uses injection moulding method to manufacture the goods such as sole, moral
The research of this respect was once done by Bayer company of state.Heat preservation plate material, by waste polyurethane foam plastics after coarse crushing, wherein
Add adhesive, water, agitated enter mould, apply certain pressure, keep certain temperature, after the time, the demoulding prepares warming plate
Material.The method has that technique is simple, low cost and be of value to the advantages such as environmental protection.The extensive chromatic steel sandwich plate of warming plate that obtains, in
The fields such as centre air-conditioning, construction material, freezer, cold room, couveuse, chemical tank.As filler, useless refrigerator, refrigerator-freezer are torn open
The foam that solution is got off, the hard polyurethane foams of bulk, after checking its performance qualified, as small refrigerator or other equipment
Heat-insulation layer, remaining particle is included in fritter hard PU foam process；It is crushed to certain particle size the most respectively, as filling out
Material.Various waste polyurethanes are ground into shred or powder and reuse as filler absorption raw material reclaims.According to The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640,
Report, waste polyurethane is reused in production RIM goods ratio new raw material low cost as filler.
Chemical recovery techniques: chemical method is by various methods by the monomer dissociation in polymer out, by fractional distillation etc.
Monomer separation out or is added the method that other compositions prepare product by means.Chemical recovery techniques has been summed up 6 kinds: alcohol
Solution, Hydrolyze method, alkaline hydrolysis, ammonolysis process, pyrolysismethod, hydrocracking process.Catabolite produced by various methods is different.Alcoholysis
Method, generally generates polyol blends.With alcohol compound as distintegrant, in case of heating, polyurethane waste material is decomposed
For the method for polyether polyol, it is alcoholysis method.Polyurethane waste material dihydroxylic alcohols is alcoholysis agent, protects in moderate temperature and gas
Protecting lower reaction and be degraded to low molecular polylol etc., catabolite is stable, forms simpler, it is easy to separate and purification.For hard
Polyurethane foam plastics, compare and be suitable for using alcoholysis method PROCESS FOR TREATMENT, be characterized in that alcoholysis conditions is gentle, response speed compares water
Solution, pyrolysismethod are low, it is allowed to waste material contains other impurity.Hydrolyze method, generates polyhydric alcohol and polyamine.Hydrolyze method is to utilize alkali gold
Belong to hydroxide and make catalyst, under the effect of high-pressure steam, in 250～340 DEG C, hard polyurethane foam or soft bubble are hydrolyzed into two
Amine, polyhydric alcohol CO2.The shortcoming of this method is that hydrolysis is to carry out at high temperature under high pressure, thus to reaction condition and equipment requirements very
Height, and the purification technique difficulty of hydrolyzate is the biggest, institute is not the most widely used.Alkaline hydrolysis, raw
Become amine, alcohol and the carbonate of corresponding alkali.With alkali metal or alkaline earth metal hydroxide as degradation agent, will be poly-at 160～200 DEG C
Urethane is degraded into oligomer.The product of reaction is mainly become moderate-length carbochain, by poly-ammonia by polyether polyol, binary arylamine etc.
Ester is transformed into soft plastic material, and for soft microcellular polyurethane foam, the powder after can being pulverized is blended into thermoplastic poly ammonia
In ester, pelletize in extrusion shaping machine, use injection moulding method to manufacture the goods such as sole, this once did in Bayer company of Germany
The research of aspect.Ammonolysis process, generates polyhydric alcohol, amine, urea.Ammonolysis process refers in the supercritical state, with ammonia by polyurethane
Urea bond is cut off with urethane bonds, generates polyhydric alcohol, amine and the method for non-substituted urea.DOW Plastics Company utilizes this method
It is successfully made production.Hydrocracking process, primary product is that oil is gentle.Hydrocracking process refers to that the polyurethane after pulverizing is placed in and adds
In hydrogen reactor, it is made to be cracked into the method that oil is gentle at 40MPa and 500 DEG C.Due to economic factor, only substantial amounts of poly-
When urethane needs to process, this method is just suitable for.
Heat energy method is reclaimed in burning: polyurethane mainly contains carbon, hydrogen, oxygen, nitrogen, when burning in atmosphere, produces substantial amounts of heat
Can, per kilogram polyurethane about produces the heat of 25-28MJ.Polyurethane waste material is often and municipal solid waste one acts as fuel, can
Replace part coal and make boiler oil, it is provided that heat energy.
Added value of product prepared by Physical is relatively low, and reclaims heat energy method and easily cause secondary pollution.In chemical method, hydrolysis
The polyhydric alcohol difficulty purification that method produces, costly；Alkaline hydrolysis technique is long, and cost is high；The product component that amine-decomposing method obtains is complicated, unfavorable
In recycling；Alcohol reaction can normal pressure, under the conditions of carry out, but degradation temperature is of a relatively high.
Summary of the invention
It is an object of the invention to provide the recycling work that a kind of resolution ratio is high, recycle convenient waste polyurethane
Skill.
The present invention is achieved through the following technical solutions: the recovery processing technique of a kind of waste polyurethane, including following
Step:
Step S1: waste polyurethane is ground into polyurethane particles；
Step S2: polyurethane particles, water, antioxidant, distintegrant and catalyst are added in reactor, and is passed through indifferent gas
Body is protected, and is heated up by reactor in salt bath, 218 ~ 399 DEG C, keep 3 ~ 5 hours under the conditions of 50 ~ 150kPa, catalyst
Select carbodiimide, finally give diamine, polyhydric alcohol and carbon dioxide；
Step S3: separating binary amine and polyhydric alcohol.
In described step S3, through distillation and extraction and recovery diamine, reclaim polyhydric alcohol by rectification.
Described distintegrant include BDO, 1,2-PD, diethylene glycol, diethylene glycol, dipropylene glycol, new penta 2
One or more combinations in alcohol, methyl propanediol.
The consumption of described distintegrant is 1.5 ~ 2 times of polyurethane particles.
Described antioxidant is hindered phenol anti-oxidants.
In described step S2, in reactor, it is added with Lithium hydrate.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) by the present invention in that with carbodiimide as catalyst, it is possible in reactor, during reaction, promote product layering, improve
The activity of product and the response rate of raising polyurethane so that the chemicals quantity of recovery is many, kind complete, and can reduce institute
The temperature needed, is conducive to saving production cost, by using carbodiimide to improve diamine and the activity of polyhydric alcohol, is conducive to subtracting
Less by using the time needed for diamine and polyhydric alcohol resynthesis polyurethane and catalyst, be conducive to saving production cost,
Use with antioxidant collocation, it is possible to avoid diamine and polyhydric alcohol oxidized；
(2) by the present invention in that and with salt bath, reactor heated up, its have intensification quickly, easy control of temperature, to temperature
When being adjusted, the response advantage such as quickly, is conducive to shortening rising gentle cool time, improves production efficiency with this；
(3) present invention can effectively accelerate hydrolysis by adding Lithium hydrate, advantageously reduces the temperature needed for hydrolysis,
And reduce the energy consumption needed for hydrolysis.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment:
A kind of recovery processing technique of waste polyurethane, including following step:
Step S1: waste polyurethane is ground into polyurethane particles；
Step S2: polyurethane particles, water, antioxidant, Lithium hydrate, distintegrant and catalyst are added in reactor, logical
Cross interpolation Lithium hydrate and can effectively accelerate hydrolysis, advantageously reduce the temperature needed for hydrolysis, and it is required to reduce hydrolysis
Energy consumption, and be passed through noble gas and protect, reactor is heated up in salt bath, 218 ~ 399 DEG C, 50 ~ 150kPa condition
Lower holding 3 ~ 5 hours, catalyst selection carbodiimide, distintegrant can select BDO, 1,2-PD, diethyl two
One or more combinations in alcohol, diethylene glycol, dipropylene glycol, neopentyl glycol, methyl propanediol, the consumption of distintegrant is polyurethane
1.5 ~ 2 times of granule, described antioxidant is hindered phenol anti-oxidants, finally gives diamine, polyhydric alcohol and titanium dioxide
Carbon, by using carbodiimide as catalyst, it is possible to promotes product layering in reactor during reaction, improves the activity of product
And improve the response rate of polyurethane so that the chemicals quantity of recovery is many, kind complete, and can reduce required temperature,
Be conducive to saving production cost, by using carbodiimide to improve diamine and the activity of polyhydric alcohol, advantageously reduce by making
With the time needed for diamine and polyhydric alcohol resynthesis polyurethane and catalyst, be conducive to saving production cost, with antioxidation
Agent collocation uses, it is possible to avoid diamine and polyhydric alcohol oxidized, and by using salt bath to heat up reactor, it has liter
Temperature quickly, easy control of temperature, the response advantage such as quickly time temperature is adjusted, be conducive to shortening when rising gentleness cooling with this
Between, improve production efficiency；
Step S3: separating binary amine and polyhydric alcohol, through distillation and extraction and recovery diamine, reclaims polyhydric alcohol by rectification.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on
Any simple modification of being made above example according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (6)
1. the recovery processing technique of a waste polyurethane, it is characterised in that: include following step:
Step S1: waste polyurethane is ground into polyurethane particles；
Step S2: polyurethane particles, water, antioxidant, distintegrant and catalyst are added in reactor, and is passed through indifferent gas
Body is protected, and is heated up by reactor in salt bath, 218 ~ 399 DEG C, keep 3 ~ 5 hours under the conditions of 50 ~ 150kPa, catalyst
Select carbodiimide, finally give diamine, polyhydric alcohol and carbon dioxide；
Step S3: separating binary amine and polyhydric alcohol.
The recovery processing technique of a kind of waste polyurethane the most according to claim 1, it is characterised in that: described step S3
In, through distillation and extraction and recovery diamine, reclaim polyhydric alcohol by rectification.
The recovery processing technique of a kind of waste polyurethane the most according to claim 1, it is characterised in that: described distintegrant
Including in BDO, 1,2-PD, diethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, methyl propanediol
Plant or multiple combination.
The recovery processing technique of a kind of waste polyurethane the most according to claim 1, it is characterised in that: described distintegrant
Consumption is polyurethane particles 1.5 ~ 2 times.
The recovery processing technique of a kind of waste polyurethane the most according to claim 1, it is characterised in that: described antioxidation
Agent is hindered phenol anti-oxidants.
The recovery processing technique of a kind of waste polyurethane the most according to claim 1, it is characterised in that: described step S2
In, it is added with Lithium hydrate in reactor.
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| CN201610660341.0A CN106279760A (en) | 2016-08-12 | 2016-08-12 | A kind of recovery processing technique of waste polyurethane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724305A (en) * | 2019-09-26 | 2020-01-24 | 烟台正海合泰科技股份有限公司 | Method and device for recycling composite PU foam leftover materials |
| CN113853398A (en) * | 2019-05-27 | 2021-12-28 | 科思创知识产权两合公司 | Method for producing chemical raw materials for producing isocyanates and polyurethanes by using polyurethane material waste |
| WO2022128871A1 (en) | 2020-12-14 | 2022-06-23 | Covestro Deutschland Ag | Process for recovering raw materials from polyurethane foams |
| CN114920985A (en) * | 2022-05-16 | 2022-08-19 | 广东省科学院资源利用与稀土开发研究所 | Method for recovering low-molecular-weight polyol by catalytic degradation of spandex with rare earth |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113853398A (en) * | 2019-05-27 | 2021-12-28 | 科思创知识产权两合公司 | Method for producing chemical raw materials for producing isocyanates and polyurethanes by using polyurethane material waste |
| CN110724305A (en) * | 2019-09-26 | 2020-01-24 | 烟台正海合泰科技股份有限公司 | Method and device for recycling composite PU foam leftover materials |
| CN110724305B (en) * | 2019-09-26 | 2022-02-11 | 烟台正海合泰科技股份有限公司 | Method and device for recycling composite PU foam leftover materials |
| WO2022128871A1 (en) | 2020-12-14 | 2022-06-23 | Covestro Deutschland Ag | Process for recovering raw materials from polyurethane foams |
| CN114920985A (en) * | 2022-05-16 | 2022-08-19 | 广东省科学院资源利用与稀土开发研究所 | Method for recovering low-molecular-weight polyol by catalytic degradation of spandex with rare earth |
| CN114920985B (en) * | 2022-05-16 | 2023-09-01 | 广东省科学院资源利用与稀土开发研究所 | Method for recycling low-molecular polyol by catalyzing and degrading spandex through rare earth |
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