CN102618010B - Continuous production device and method for regenerating polyol by depolymerizing waste polyurethane - Google Patents
Continuous production device and method for regenerating polyol by depolymerizing waste polyurethane Download PDFInfo
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- CN102618010B CN102618010B CN201210059689.6A CN201210059689A CN102618010B CN 102618010 B CN102618010 B CN 102618010B CN 201210059689 A CN201210059689 A CN 201210059689A CN 102618010 B CN102618010 B CN 102618010B
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Abstract
The invention discloses a continuous device for regenerating polyol by depolymerizing waste polyurethane, which comprises an extruder, a homogenous tank and a stage microwave reactor which are sequentially connected. The invention also discloses a method using the device, which comprises the following steps that: (1) the waste polyurethane is added into the extruder, and the extruder is preheated to 220 DEG C in advance; (2) an antioxidant, a catalyst, and 40 to 60% alcoholysis agent are added into the extruder; (3) a viscous semi-finished product flowing out of the extruder flows into the homogenous tank, and the remaining alcoholysis agent is added to be uniformly stirred; (4) a material in the homogenous tank is pumped to the stage microwave reactor, a treating agent is added, and the flow rate is controlled, so that the time that the material enters an inlet of the stage microwave reactor to an outlet of the stage microwave reactor is 10-20 minutes; and (5) the final finished product polyol flows out of the outlet of the stage microwave reactor. The polyether polyol generated by the method and the device has the advantages of good performance, short production cycle, high efficiency and low energy consumption.
Description
Technical field
The present invention relates to the recovery and utilization technology field of waste polyurethane, be specifically related to a kind of apparatus and method of utilizing waste polyurethane regenerating polyol.
Background technology
Urethane (being called for short PU) is the polymkeric substance of being made by raw materials such as the chainextenders such as polyisocyanates and polyether glycol or polyester polyol and/or small molecules polyvalent alcohol, polyamine or water or linking agents.Polyurethane product is widely used in many fields such as footwear, synthetic leather, fabric, medical treatment, agricultural.Along with the purposes of polyurethane material in national economy is more and more wider, consumption is increasing, and the recycling of its waste is also subject to people's attention day by day.
The recycling of current urethane mainly contains three kinds of methods: Physical, chemical method, energy law.The existing many reports of Physical and practical technique, the product properties that the PU that the method reclaims produces is poor, is only applicable to low-grade goods.Energy recovery is that this mode can cause secondary pollution, does not substantially re-use by waste material being burned to reclaim heat.Chemical method refers to that urethane resin, under the effect of chemical degradation agent, is degraded into the composition of low relative molecular mass.The DeR of urethane mainly contains alcoholysis method, ammonolysis process, pyrolysis method, alkaline hydrolysis, phosphoric acid ester method etc.Wherein alcoholysis method is a kind of most important method in chemical degradation urethane, its principle is by the scission of links such as a large amount of amino-formate bonds, urea groups and ehter bond that contain in polyurethane macromolecular, make its form relative molecular mass less containing polyester or polyether glycol, have the liquid mixture of a small amount of amine, then separating-purifying, then be blended in new PU raw material and make finished product according to the ratio lower than 20%.
In current waste polyurethane alcoholysis process, direct reacting by heating in traditional reactor normally, this technique is batch production, and the production cycle is long, energy consumption is high, utilization ratio is low, product performance are low.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, a kind of continuous production device and method of disaggregation of waste and old urethane regenerating polyol is provided, to shorten the production cycle and to reduce energy consumption.
Technical scheme of the present invention is as follows:
A continuous production device for disaggregation of waste and old urethane regenerating polyol, comprises forcing machine, homogeneous tank and segmentation microwave reactor, and wherein said forcing machine, homogeneous tank and segmentation microwave reactor are connected successively; Segmentation microwave reactor comprises and contains separately the processing leading portion of microwave generator and process back segment, processes leading portion and be provided with treatment agent entrance with the junction of processing back segment.
Preferably, enter the speed of segmentation microwave reactor in order more accurately to control material, described continuous production device also comprises pump, and homogeneous tank is connected with segmentation microwave reactor by pump.
The effect of forcing machine is the pre-mixing of carrying out material, and for reach the effect of comminuted solids material when mixing simultaneously, forcing machine is selected twin screw extruder, is provided with solid material entrance and liquid material entrance on forcing machine, to add respectively solid material and liquid material; Homogeneous tank is a kind of stirrer, and effect is that material is carried out to degree of depth mixing, so that material can react better in segmentation microwave reactor, is provided with alcoholysis agent entrance on homogeneous tank, adds the object of alcoholysis agent to realize segmentation.
Segmentation microwave reactor is the final place that alcoholysis reaction is carried out, and is to contain processing leading portion and processes back segment with the difference of traditional microwave reactor, can set respectively two different temperature of reaction, to realize the object of zone heating.Its embodiment has multiple, preferred version provided by the invention is: process leading portion and comprise the first heating chamber that is equipped with the first microwave generator and the first shielding unit, process back segment and comprise the second heating chamber that is equipped with the second microwave generator and secondary shielding device, the first heating chamber and the second heating chamber are separated by the first shielding unit and secondary shielding device, and treatment agent entrance is arranged between the first heating chamber and the second heating chamber.In this scheme, the first heating chamber and the second heating chamber form two independently microwave heating chamber, and the microwave that the first heating chamber and the second heating chamber produce separately can not enter adjacent heating chamber each other, by the first microwave generator and the second microwave generator are arranged to different power, can realize two different temperature of reaction.
The continuous production method of disaggregation of waste and old urethane regenerating polyol provided by the invention, use above-mentioned continuous production device and carry out according to the following steps:
(1) waste polyurethane is added to forcing machine, forcing machine is preheated to 220 ℃ in advance;
(2) in forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 40 ~ 60%;
(3) the thick work in-process that flow out from forcing machine enter homogeneous tank, add remaining alcoholysis agent, in homogeneous tank, stir;
(4) material in homogeneous tank is pumped in segmentation microwave reactor, add treatment agent, coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10-20 minute;
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
While containing pump in continuous production device, step pumps to the material in homogeneous tank in segmentation microwave reactor with pump in (4).
Preferably, in step (2), in forcing machine, the residence time of material is 10 minutes; The time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes in step (4); The temperature of reaction of processing leading portion in segmentation microwave reactor is 190-230 ℃, and the temperature of reaction of processing back segment is 80-150 ℃.
The liquid material that step (2) adds, comprises alcoholysis agent, antioxidant and catalyzer, and proportioning is by weight: 100 parts of waste polyurethanes, alcoholysis agent 40-200 part, catalyzer 0.03-5 part, antioxidant 0.03-3 part, treatment agent 3-80 part.
According to above-mentioned formula rate, if disposable, all add alcoholysis agent, the work in-process that forcing machine obtains are flow-like, in screw rod, can not effectively mediate and promote to extrude, therefore the present invention also realizes by being provided with the homogeneous tank of alcoholysis agent entrance the object that segmentation adds alcoholysis agent, so that material fully mixes and have lower viscosity, then enter segmentation microwave reactor and react.
Wherein, described waste polyurethane is the waste material producing in polyurathamc manufacturing processed, be the porous blister polyurethane material being formed by multicomponent isocyanate and polyvalent alcohol raw material reaction, it is the flap of length below 3cm after pulverizing for pattern of the present invention.The recovery polyurethane material of not getting rid of other forms is also applicable to the technology of the present invention.The polyvalent alcohol that reaction obtains is aqueous homogeneous mixture.
Wherein, described alcoholysis agent is molecular weight 62-2000, hydroxy functionality is fatty alcohol or polyether glycol or the polyester diol of 2-3, include but not limited to ethylene glycol, propylene glycol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, 1, 8-ethohexadiol, glycerine, TriMethylolPropane(TMP), 1, 4-hydroxymethyl-cyclohexane, Hydrogenated Bisphenol A, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, the copolymerization ether alcohol of ethylene glycol and propylene glycol, poly-1, 4-butyleneglycol, glycerine causes the polyether-tribasic alcohol of oxyethane open loop gained, glycerine causes the polyether-tribasic alcohol of propylene oxide open loop gained, TriMethylolPropane(TMP) causes the polyether-tribasic alcohol of oxyethane open loop gained, TriMethylolPropane(TMP) causes the polyether-tribasic alcohol of propylene oxide open loop gained, hydroxyethoxylation dihydroxyphenyl propane, propoxyl dihydroxyphenyl propane.
Preferably, the low-molecular-weight polyester dibasic alcohol that the aliphatic dialcohol that described polyester diol is is 62-600 by di-carboxylic acid or its corresponding dicarboxylic acid anhydride and molecular weight or polyether glycol obtain based on conventional esterification condensation, the molecular weight of polyester diol is 150-2000, and the described dicarboxylic acid anhydride for the synthesis of low-molecular-weight polyester dibasic alcohol comprises Tetra hydro Phthalic anhydride, maleic anhydride, Succinic anhydried, tetrahydrophthalic anhydride, HHPA; Aliphatic dialcohol or polyether glycol for the synthesis of low-molecular-weight polyester dibasic alcohol include but not limited to ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, Hydrogenated Bisphenol A, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hydroxyethoxylation dihydroxyphenyl propane, propoxyl dihydroxyphenyl propane.
Described antioxidant consists of following weight part: four [b-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2-3 part, 1 part of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Described catalyzer consists of following weight part: 1 part of organo-metallic catalyst, tertiary amine catalyst 0.5-2 part.
Preferably, the sodium that described organo-metallic salt catalyst is 2-4 carbon atom carboxylic acid, potassium, zinc, manganese metal-salt, comprise Potassium ethanoate, sodium-acetate, zinc acetate, manganese acetate, potassium acrylate, sodium acrylate, zinc acrylate resin, toxilic acid monopotassium salt, toxilic acid zinc salt; Nitrogen-atoms in described tertiary amine catalyst is connected with three alkyl that contain 2-4 carbon atom, and wherein at least one alkyl with hydroxyl, described tertiary amine catalyst includes but not limited to trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-sec.-propyl diethanolamine, N-normal-butyl diethanolamine, tripropanol amine, N-methyl dipropanolamine, N-ethyl dipropanolamine, N-sec.-propyl dipropanolamine, N-normal-butyl dipropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethyl propanol amine, N, N-diethylpropanolamine.
Preferably, described treatment agent is acid anhydrides or the compound at least with a carboxyl, can be that the salt of carboxyl is, the ester of carboxyl and epoxy compounds include but not limited to formic acid, acetic acid, propionic acid, oxalic acid, toxilic acid, propanedioic acid, phthalic acid, diacetyl oxide, Tetra hydro Phthalic anhydride, sodium formiate and analogue, lime acetate and analogue, methyl acetate, ethyl acetate and analogue.
The object that adds treatment agent is to carry out aftertreatment, to lower reactive behavior.Traditional method speed of response is too fast, is difficult in practice application.According to proportioning of the present invention add after treatment agent can be when not affecting product physicochemical property the suitable inhibited reaction time, make this technique have more practicality and operability.
The present invention uses unique technical formula, is equipped with continuous production device, thereby reaches the object of continuous depolymerization waste polyurethane regenerating polyol.During operation, only need feed in raw material and control the flow velocity in each device by proportion scale, can obtain incessantly polyvalent alcohol finished product.Compare with the batch production method of prior art, the continuous production method that device of the present invention provides can make the production cycle foreshorten to 35% original left and right.Produce the polyvalent alcohol finished product of 1 ton, traditional batch formula method needs 11 ~ 13 hours, and uses continuous production device of the present invention only to need 2 ~ 4 hours, and efficiency improves greatly.
Compared with prior art, the present invention has following beneficial effect:
(1) use unique technical formula, the polyether glycol performance of regenerating is good;
(2) in segmentation microwave reactor, carry out alcoholysis reaction, the reaction times is short, makes that product purity is high, by product is few, and energy consumption is low, non-environmental-pollution, has shortened the production cycle of whole device;
(3) device continuously-running, enhances productivity greatly.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of continuous production device of the present invention;
Fig. 2 is another schematic diagram of continuous production device of the present invention;
Fig. 3 is the partial view of an embodiment of segmentation microwave reactor of the present invention.
Embodiment
With reference to Fig. 1 construction device.Twin screw extruder 1, homogeneous tank 2 and segmentation microwave reactor 3 are connected successively: solid material entrance and liquid material entrance are set on forcing machine 1, on homogeneous tank 2, be provided with alcoholysis agent entrance, segmentation microwave reactor 3 comprises and contains separately the processing leading portion 31 of microwave generator and process back segment 32, processes leading portion 31 and process back segment 32 junction being provided with treatment agent entrance 33.The outlet of forcing machine 1 is connected with the import of homogeneous tank 2, and the outlet of homogeneous tank 2 is connected to the import of segmentation microwave reactor 3, obtains the continuous production device of disaggregation of waste and old urethane regenerating polyol.
Wherein segmentation microwave reactor 3 arranges with reference to Fig. 3.Process leading portion 31 and comprise the first heating chamber 301 that is equipped with the first microwave generator 311 and the first shielding unit 321, process back segment 32 and comprise the second heating chamber 302 that is equipped with the second microwave generator 312 and secondary shielding device 322, the first heating chamber 301 and the second heating chamber 302 are separated by the first shielding unit 321 and secondary shielding device 322, and treatment agent entrance 33 is arranged between the first heating chamber 301 and the second heating chamber 302.
embodiment 2
With reference to Fig. 2 construction device.Twin screw extruder 1, homogeneous tank 2, pump 4 and segmentation microwave reactor 3 are connected successively: solid material entrance and liquid material entrance are set on forcing machine 1, on homogeneous tank 2, be provided with alcoholysis agent entrance, segmentation microwave reactor 3 comprises and contains separately the processing leading portion 31 of microwave generator and process back segment 32, processes leading portion 31 and process back segment 32 junction being provided with treatment agent entrance 33.The outlet of forcing machine 1 is connected with the import of homogeneous tank 2, and the outlet of homogeneous tank 2 is connected to the fluid inlet of pump 4, and the liquid outlet of pump 4 is connected to the import of segmentation microwave reactor 3, obtains the continuous production device of disaggregation of waste and old urethane regenerating polyol.
Wherein segmentation microwave reactor 3 arranges with reference to Fig. 3.Process leading portion 31 and comprise the first heating chamber 301 that is equipped with the first microwave generator 311 and the first shielding unit 321, process back segment 32 and comprise the second heating chamber 302 that is equipped with the second microwave generator 312 and secondary shielding device 322, the first heating chamber 301 and the second heating chamber 302 are separated by the first shielding unit 321 and secondary shielding device 322, and treatment agent entrance 33 is arranged between the first heating chamber 301 and the second heating chamber 302.
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, BDO 40g;
Sodium-acetate 0.1g, trolamine 1.0g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 0.05g;
Acetic acid 5g
Use the continuous production device of embodiment 2 structures and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 40%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) with pump, the material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.5mgKOH/g, viscosity 2400cps, hydroxyl value is about 350mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 3 hours.
embodiment 4
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, propylene glycol 80g;
Zinc acrylate resin 0.1g, trolamine 0.2g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 0.1g;
Propionic acid 10g,
Use the continuous production device of embodiment 2 structures and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 50%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) with pump, the material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.75mgKOH/g, viscosity 800cps, hydroxyl value is about 450mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 3 hours.
embodiment 5
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, Hydrogenated Bisphenol A 100g;
Toxilic acid monopotassium salt 0.1g, N methyldiethanol amine 0.2g;
By 3 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 0.2g;
Acetic acid 5g,
Use the continuous production device of embodiment 1 structure and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 60%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.75mgKOH/g, viscosity 3800cps, hydroxyl value is about 160mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 2.5 hours.
embodiment 6
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, glycerol 100g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 0.2g;
Propionic acid 10g,
Use the continuous production device of embodiment 2 structures and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 50%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) with pump, the material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 20 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.85mgKOH/g, viscosity 500cps, hydroxyl value is about 300mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 4 hours.
embodiment 7
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, the polyoxyethylene glycol 150g that molecular weight is 1000;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 0.2g;
Propionic acid 10g,
Use the continuous production device of embodiment 2 structures and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 50%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) with pump, the material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 12 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.4mgKOH/g, viscosity 850cps, hydroxyl value is about 80mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 3 hours.
embodiment 8
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, the glycerine that molecular weight is 2000 causes oxyethane open loop gained polyether-tribasic alcohol 200g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 2g;
Acetic acid 5g,
Use the continuous production device of embodiment 1 structure and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 40%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.4mgKOH/g, viscosity 1350cps, hydroxyl value is about 65mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 3 hours.
embodiment 9
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, the polyester diol 200g that is 2000 by Tetra hydro Phthalic anhydride and the synthetic molecular weight of 1,6-hexylene glycol;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1 part forms antioxidant, takes 2g;
Acetic acid 5g,
Use the continuous production device of embodiment 1 structure and react according to the following steps:
(1) waste polyurethane foam particle is joined to the solid material entrance of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material entrance of forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 60%, the residence time is 10 minutes;
(3) the thick work in-process that flow out from the outlet of forcing machine enter into homogeneous tank, add remaining alcoholysis agent, heated and stirred in homogeneous tank;
(4) material in homogeneous tank is pumped in segmentation microwave reactor, by setting the power of the first microwave generator, the temperature of reaction that makes to process leading portion is 190-230 ℃, by setting the power of the second microwave generator, the temperature of reaction that makes to process back segment is 80-150 ℃, reacts.And coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 18 minutes.
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
The aqueous homogeneous mixture of gained polyvalent alcohol, the acid number of gained polyvalent alcohol is about 0.75mgKOH/g, viscosity 2100cps, hydroxyl value is about 74mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 3.5 hours.
comparative example 1
Segmentation microwave reactor in embodiment 4 is changed to conventional reactor heating and adopts conventional reaction process; the each component that is about to prepare burden stirs to obtain compound jointly; under the protection of nitrogen; control 210 ℃-220 ℃ reactions of temperature 5 hours, gained polyol blends darkens, and urethane solid particulate does not dissolve completely; acid number is about 1.5mgKOH/g; viscosity 1500cps, hydroxyl value is about 500mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 12 hours.
comparative example 2
Segmentation microwave reactor in embodiment 9 is changed to conventional reactor heating and adopts conventional reaction process; the each component that is about to prepare burden stirs to obtain compound jointly; under the protection of nitrogen; control 210 ℃-220 ℃ reactions of temperature 5 hours, gained polyol blends darkens, and urethane solid particulate does not dissolve completely; acid number is about 1.8mgKOH/g; viscosity 4500cps, hydroxyl value is about 85mgKOH/g, and obtaining 1 ton of polyvalent alcohol required time is 11 hours.
Claims (9)
1. the continuous production device of a disaggregation of waste and old urethane regenerating polyol, it is characterized in that: comprise forcing machine (1), homogeneous tank (2) and segmentation microwave reactor (3), wherein said forcing machine (1), homogeneous tank (2) and segmentation microwave reactor (3) are connected successively; Segmentation microwave reactor (3) comprises processing leading portion (31) and the processing back segment (32) that contains separately microwave generator, and the junction of processing leading portion (31) and processing back segment (32) is provided with treatment agent entrance (33).
2. continuous production device as claimed in claim 1, characterized by further comprising pump (4), and homogeneous tank (2) is connected with segmentation microwave reactor (3) by pump (4).
3. continuous production device as claimed in claim 1, is characterized in that described forcing machine (1) is twin screw extruder.
4. continuous production device as claimed in claim 1, the processing leading portion (31) that it is characterized in that described segmentation microwave reactor (3) comprises the first heating chamber (301) that is equipped with the first microwave generator (311) and the first shielding unit (321), process back segment (32) and comprise the second heating chamber (302) that is equipped with the second microwave generator (312) and secondary shielding device (322), the first heating chamber (301) and the second heating chamber (302) are separated by the first shielding unit (321) and secondary shielding device (322), treatment agent entrance (33) is arranged between the first heating chamber (301) and the second heating chamber (302).
5. a continuous production method for disaggregation of waste and old urethane regenerating polyol, is characterized in that right to use requires in 1-4 the continuous production device described in any one and carries out according to the following steps:
(1) waste polyurethane is added to forcing machine, forcing machine is preheated to 220 ℃ in advance;
(2) in forcing machine, add the alcoholysis agent of antioxidant, catalyzer and 40 ~ 60%;
(3) the thick work in-process that flow out from forcing machine enter homogeneous tank, add remaining alcoholysis agent, in homogeneous tank, stir;
(4) material in homogeneous tank is pumped in segmentation microwave reactor, add treatment agent, coutroi velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10-20 minute;
(5) final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
6. continuous production method as claimed in claim 5, is characterized in that with pump, the material in homogeneous tank being pumped in segmentation microwave reactor in step (4).
7. continuous production method as claimed in claim 5, is characterized in that the time from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor of material in step (4) is 15 minutes.
8. continuous production method as claimed in claim 5, is characterized in that the temperature of reaction of processing leading portion in segmentation microwave reactor is 190-230 ℃, and the temperature of reaction of processing back segment is 80-150 ℃.
9. continuous production method as claimed in claim 5, is characterized in that proportioning is by weight: 100 parts of waste polyurethanes, alcoholysis agent 40-200 part, catalyzer 0.03-5 part, antioxidant 0.03-3 part, treatment agent 3-80 part.
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| CN106279756A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The polyurethane contained in diethylene glycol alcoholysis removal Waste Polyester textile is for the method for polyester spinning melts |
| CN106283228A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The method that the polyurethane contained in Waste Polyester textile carries out Direct-spinning of PET Fiber is removed in a kind of alcoholysis |
| CN107602911A (en) * | 2017-10-18 | 2018-01-19 | 上海第二工业大学 | A kind of method of microwave radiation technology alcoholysis waste refrigerators polyurethane |
| CN109320764B (en) * | 2018-09-14 | 2021-04-06 | 烟台正海合泰科技股份有限公司 | Industrialized pure PU foam alcoholysis recovery method and special recovery feeding device |
| KR20230138359A (en) * | 2022-03-23 | 2023-10-05 | 주식회사 엘지화학 | Method for preparing recycled abs resin |
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| CN1180689A (en) * | 1996-10-08 | 1998-05-06 | 三星电子株式会社 | Method for preparation of recycled polyols and method for manufacturing polyurethane foams therefrom |
| CN202490612U (en) * | 2012-03-08 | 2012-10-17 | 广州聚天化工科技有限公司 | Continuous production device for depolymerizing waste polyurethane and regenerating polyatomic alcohol |
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| CN1180689A (en) * | 1996-10-08 | 1998-05-06 | 三星电子株式会社 | Method for preparation of recycled polyols and method for manufacturing polyurethane foams therefrom |
| CN202490612U (en) * | 2012-03-08 | 2012-10-17 | 广州聚天化工科技有限公司 | Continuous production device for depolymerizing waste polyurethane and regenerating polyatomic alcohol |
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| JP特开平11-92654A 1999.04.06 |
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