CN102618010A - 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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- CN102618010A CN102618010A CN2012100596896A CN201210059689A CN102618010A CN 102618010 A CN102618010 A CN 102618010A CN 2012100596896 A CN2012100596896 A CN 2012100596896A CN 201210059689 A CN201210059689 A CN 201210059689A CN 102618010 A CN102618010 A CN 102618010A
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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 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 regeneration polyvalent alcohol.
Background technology
Urethane (be called for short PU) is the polymkeric substance of being processed by raw materials such as chainextender such as POLYMETHYLENE POLYPHENYLISOCYANATE and polyether glycol or polyester polyol 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 also receives people's attention day by day.
The recycling of current urethane mainly contains three kinds of methods: physics method, chemical method, energy law.Existing many reports of physics method and practical technique, the product properties that the PU that this method reclaims produces is relatively poor, only is applicable to low-grade goods.Energy recovery is to reclaim heat through waste material is burned, and this mode can cause secondary pollution, does not re-use basically.Chemical method is meant 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, pyrogenic silica, alkaline hydrolysis method, SULPHOSUCCINIC ACID ESTER method etc.Wherein alcoholysis method is most important a kind of method in the chemical degradation urethane; Its principle is with the scission of links such as a large amount of amino-formate bonds, urea groups and ehter bond that contain in the polyurethane macromolecular; Make its form relative molecular mass less contain the liquid mixture that polyester or polyether glycol have small amount of amine; Separate then and purify, be blended in the new PU raw material according to the ratio that is lower than 20% again and process finished product.
In the present waste polyurethane alcoholysis process, direct reacting by heating in traditional reaction kettle normally, this technology 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 objective of the invention is to overcome the defective of above-mentioned prior art, a kind of continuous production apparatus and method of disaggregation of waste and old urethane regeneration polyvalent alcohol are provided, to shorten the production cycle and to cut down the consumption of energy.
Technical scheme of the present invention is following:
A kind of continuous production device of disaggregation of waste and old urethane regeneration polyvalent alcohol comprises forcing machine, even matter jar and segmentation microwave reactor, and wherein said forcing machine, even matter jar are connected with the segmentation microwave reactor successively; The segmentation microwave reactor comprises the processing leading portion and processing back segment that contains microwave generator separately, handles leading portion and is provided with the treatment agent inlet with the junction of handling back segment.
Preferably, in order more accurately to control the speed that material gets into the segmentation microwave reactor, said continuous production device also comprises pump, and even matter jar is connected with the segmentation microwave reactor through pump.
The effect of forcing machine is the pre-mixing of carrying out material, and for when mixing, reaching the effect of comminuted solids material simultaneously, forcing machine is selected twin screw extruder for use, and forcing machine is provided with solid material inlet and liquid material inlet, to add solid material and liquid material respectively; Even matter jar is a kind of stirrer, and effect is material to be carried out the degree of depth mix, so that material can react in the segmentation microwave reactor better, even matter jar is provided with alcoholysis agent inlet, adds the purpose of alcoholysis agent to realize segmentation.
The segmentation microwave reactor is the final place that alcoholysis reaction is carried out, and is to contain with the difference of traditional microwave reactor drum and handles leading portion and handle back segment, can set two different temperature of reaction respectively, to realize the purpose of zone heating.Its embodiment has multiple; Preferred version provided by the invention is: handle leading portion and comprise first heating chamber that is equipped with first microwave generator and first shielding unit; Handle back segment and comprise second heating chamber that is equipped with second microwave generator and secondary shielding device; First heating chamber and second heating chamber are separated by first shielding unit and secondary shielding device, and the treatment agent inlet is arranged between first heating chamber and second heating chamber.First heating chamber and second heating chamber form two independently microwave heating chamber in this scheme; And the microwave that first heating chamber and second heating chamber produce separately can not get into adjacent heating chamber each other; Through first microwave generator and second microwave generator are provided with different power, can realize two different temperature of reaction.
The continuous production method of disaggregation of waste and old urethane provided by the invention regeneration polyvalent alcohol, use above-mentioned continuous production device and carry out according to the following steps:
(1) waste polyurethane is added forcing machine, forcing machine is preheated to 220 ℃ in advance;
(2) in forcing machine, add the alcoholysis agent of inhibitor, catalyzer and 40 ~ 60%;
(3) get into even matter jar from the effusive thick work in-process of forcing machine, add remaining alcoholysis agent, in even matter jar, stir;
(4) material that will spare in the matter jar pumps in the segmentation microwave reactor, adds treatment agent, the control flow velocity, and making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10-20 minute;
(5) the final finished polyvalent alcohol flows out from the outlet of segmentation microwave reactor.
When containing pump in the continuous production device, the material that will spare in the matter jar with pump in the step (4) pumps in the segmentation microwave reactor.
Preferably, the residence time of the interior material of forcing machine is 10 minutes in the step (2); The time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes in the step (4); The temperature of reaction of handling leading portion in the segmentation microwave reactor is 190-230 ℃, and the temperature of reaction of handling back segment is 80-150 ℃.
The liquid material that step (2) adds comprises alcoholysis agent, inhibitor and catalyzer, by weight proportioning be: 100 parts of waste polyurethanes, alcoholysis agent 40-200 part, catalyzer 0.03-5 part, inhibitor 0.03-3 part, treatment agent 3-80 part.
According to above-mentioned formula rate; If disposable whole adding alcoholysis agent; The work in-process that forcing machine obtains are flow-like, in screw rod, can not effectively mediate and promote to extrude, so the present invention also realize that through the even matter jar that is provided with alcoholysis agent inlet segmentation adds the purpose of alcoholysis agent; So that material thorough mixing and have lower viscosity gets into the segmentation microwave reactor again and reacts.
Wherein, Described waste polyurethane is the waste material that produces in the polyurathamc manufacturing processed; Be the porous blister polyurethane material that is formed by multicomponent isocyanate and polyvalent alcohol raw material reaction, it is used for pattern of the present invention is through pulverizing the flap of back length below 3cm.The recovery polyurethane material of not getting rid of other forms also is fit to the present invention's technology.The polyvalent alcohol that reaction obtains is aqueous homogeneous mixture.
Wherein, Described alcoholysis agent is that molecular weight 62-2000, hydroxy functionality are Fatty Alcohol(C12-C14 and C12-C18) or polyether glycol or the polyester diol of 2-3; Include but not limited to terepthaloyl moietie, Ucar 35,1; 4-butyleneglycol, 1; 6-pinakon, 1; 8-ethohexadiol, glycerine, TriMethylolPropane(TMP), 1, gather 1 at the copolymerization ether alcohol of 4-hydroxymethyl-cyclohexane, Hydrogenated Bisphenol A 99, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, W 166, terepthaloyl moietie and Ucar 35, and 4-butyleneglycol, glycerine cause the polyether-tribasic alcohol of oxyethane open loop gained, the polyether-tribasic alcohol that glycerine causes propylene oxide open loop gained, the polyether-tribasic alcohol that TriMethylolPropane(TMP) causes oxyethane open loop gained, polyether-tribasic alcohol, hydroxyethoxylation dihydroxyphenyl propane, the propoxyl dihydroxyphenyl propane that TriMethylolPropane(TMP) causes propylene oxide open loop gained.
Preferably; Said polyester diol is to be the aliphatic dialcohol of 62-600 or the low-molecular-weight polyester divalent alcohol that polyether glycol gets based on conventional esterification condensation by di-carboxylic acid or its corresponding dicarboxylic acid anhydride and molecular weight; The molecular weight of polyester diol is 150-2000, and the said dicarboxylic acid anhydride that is used for synthetic low-molecular-weight polyester divalent alcohol comprises Tetra hydro Phthalic anhydride, maleic anhydride, Succinic anhydried, THPA, HHPA; The aliphatic dialcohol or the polyether glycol that are used for synthetic low-molecular-weight polyester divalent alcohol include but not limited to terepthaloyl moietie, Ucar 35,1; 4-butyleneglycol, 1; 6-pinakon, 1; 8-ethohexadiol, 1,4-hydroxymethyl-cyclohexane, Hydrogenated Bisphenol A 99, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, W 166, hydroxyethoxylation dihydroxyphenyl propane, propoxyl dihydroxyphenyl propane.
Said inhibitor is made up of following weight part: four [b-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2-3 part, 1 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
Said catalyzer is made up of following weight part: 1 part of organo-metallic catalyst, tertiary amine catalyst 0.5-2 part.
Preferably, the sodium that said 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 the said tertiary amine catalyst links to each other with three alkyl that contain 2-4 carbon atom; And wherein have hydroxyl at least one alkyl; Said tertiary amine catalyst includes but not limited to trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-sec.-propyl diethylolamine, N-normal-butyl diethylolamine, 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 that has a carboxyl at least; Can be the salt of carboxyl, the ester and the epoxy compounds of carboxyl, include but not limited to formic acid, acetate, 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, ETHYLE ACETATE and analogue.
The purpose that adds treatment agent is to carry out aftertreatment, to lower reactive behavior.The traditional method speed of response is too fast, in reality, is difficult to use.According to proportioning of the present invention add behind the treatment agent can be when not influencing the product physicochemical property appropriate inhibition reaction times, make this technology have more practicality and operability.
The present invention uses the unique technique prescription, is equipped with the serialization production equipment, thereby reaches the purpose of continuous depolymerization waste polyurethane regeneration polyvalent alcohol.Only need be during operation reinforced and control the flow velocity in each device by proportion scale, promptly can obtain the polyvalent alcohol finished product incessantly.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 original about 35%.Produce 1 ton polyvalent alcohol finished product, traditional batch formula method needs 11 ~ 13 hours, and uses continuous production device of the present invention only to need 2 ~ 4 hours, and efficient improves greatly.
Compared with prior art, the present invention has following beneficial effect:
(1) use the unique technique prescription, institute's regenerated polyether glycol performance is good;
(2) in the 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) the device continuously-running is enhanced productivity greatly.
Description of drawings
Fig. 1 is a continuous production schematic representation of apparatus of the present invention;
Fig. 2 is another synoptic 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
Embodiment 1
With reference to Fig. 1 construction device.Twin screw extruder 1, even matter jar 2 are connected with segmentation microwave reactor 3 successively: solid material inlet and liquid material inlet are set on the forcing machine 1; Even matter jar 2 is provided with alcoholysis agent inlet; Segmentation microwave reactor 3 comprises the processing leading portion 31 and processing back segment 32 that contains microwave generator separately, handles leading portion 31 and is provided with treatment agent inlet 33 with the junction of handling back segment 32.The outlet of forcing machine 1 links to each other with the import of even matter jar 2, and the outlet of even matter jar 2 is connected to the import of segmentation microwave reactor 3, promptly obtains the continuous production device of disaggregation of waste and old urethane regeneration polyvalent alcohol.
Wherein segmentation microwave reactor 3 is provided with reference to Fig. 3.Handle leading portion 31 and comprise first heating chamber 301 that is equipped with first microwave generator 311 and first shielding unit 321; Handle back segment 32 and comprise second heating chamber 302 that is equipped with second microwave generator 312 and secondary shielding device 322; First heating chamber 301 and second heating chamber 302 are separated with secondary shielding device 322 by first shielding unit 321, and treatment agent inlet 33 is arranged between first heating chamber 301 and second heating chamber 302.
Embodiment 2
With reference to Fig. 2 construction device.Twin screw extruder 1, even matter jar 2, pump 4 are connected with segmentation microwave reactor 3 successively: solid material inlet and liquid material inlet are set on the forcing machine 1; Even matter jar 2 is provided with alcoholysis agent inlet; Segmentation microwave reactor 3 comprises the processing leading portion 31 and processing back segment 32 that contains microwave generator separately, handles leading portion 31 and is provided with treatment agent inlet 33 with the junction of handling back segment 32.The outlet of forcing machine 1 links to each other with the import of even matter jar 2, and the outlet of even matter jar 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, promptly obtains the continuous production device of disaggregation of waste and old urethane regeneration polyvalent alcohol.
Wherein segmentation microwave reactor 3 is provided with reference to Fig. 3.Handle leading portion 31 and comprise first heating chamber 301 that is equipped with first microwave generator 311 and first shielding unit 321; Handle back segment 32 and comprise second heating chamber 302 that is equipped with second microwave generator 312 and secondary shielding device 322; First heating chamber 301 and second heating chamber 302 are separated with secondary shielding device 322 by first shielding unit 321, and treatment agent inlet 33 is arranged between first heating chamber 301 and second heating chamber 302.
Embodiment 3
Prepare burden by weight:
1, waste polyurethane foam plastics particle 100g, 1,4-butyleneglycol 40g;
Sodium-acetate 0.1g, trolamine 1.0g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 0.05g;
Acetic acid 5g
Use the continuous production device that embodiment 2 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 40%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar with pump pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) the 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, Ucar 35 80g;
Zinc acrylate resin 0.1g, trolamine 0.2g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 0.1g;
Propionic acid 10g,
Use the continuous production device that embodiment 2 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 50%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar with pump pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) the 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 99 100g;
Toxilic acid monopotassium salt 0.1g, N methyldiethanol amine 0.2g;
By 3 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 0.2g;
Acetic acid 5g,
Use the continuous production device that embodiment 1 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 60%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10 minutes.
(5) the 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, USP Kosher 100g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 0.2g;
Propionic acid 10g,
Use the continuous production device that embodiment 2 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 50%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar with pump pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 20 minutes.
(5) the 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, molecular weight are 1000 polyoxyethylene glycol 150g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 0.2g;
Propionic acid 10g,
Use the continuous production device that embodiment 2 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 50%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar with pump pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 12 minutes.
(5) the 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, molecular weight are 2000 glycerine initiation oxyethane open loop gained polyether-tribasic alcohol 200g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 2g;
Acetic acid 5g,
Use the continuous production device that embodiment 1 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 40%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 15 minutes.
(5) the 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, by Tetra hydro Phthalic anhydride and 1,6-pinakon synthetic molecular weight is 2000 polyester diol 200g;
Sodium-acetate 0.1g, trolamine 0.1g;
By 2 parts of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the proportioning that tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester is 1 part is formed inhibitor, takes 2g;
Acetic acid 5g,
Use the continuous production device that embodiment 1 makes up and react according to the following steps:
(1) waste polyurethane foam particle is joined the solid material inlet of forcing machine, forcing machine heats up in advance and is preheated to 220 ℃;
(2) at the liquid material of forcing machine inlet, add the alcoholysis agent of inhibitor, catalyzer and 60%, the residence time is 10 minutes;
(3) enter into even matter jar from the effusive thick work in-process of the outlet of forcing machine, add remaining alcoholysis agent, heated and stirred in even matter jar;
(4) material that will spare in the matter jar pumps in the segmentation microwave reactor; Through setting the power of first microwave generator, making the temperature of reaction of handling leading portion is 190-230 ℃, through setting the power of second microwave generator; Making the temperature of reaction of handling back segment is 80-150 ℃, reacts.And the control flow velocity, making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 18 minutes.
(5) the 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 Examples 1
Segmentation microwave reactor among the embodiment 4 is changed to conventional reactor heating and adopts conventional reaction process, the each component that is about to prepare burden stir jointly compound, under protection of nitrogen gas; 210 ℃-220 ℃ reactions of controlled temperature 5 hours, the gained polyol blends darkens, and the not dissolving fully of urethane solid particulate; 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 Examples 2
Segmentation microwave reactor among the embodiment 9 is changed to conventional reactor heating and adopts conventional reaction process, the each component that is about to prepare burden stir jointly compound, under protection of nitrogen gas; 210 ℃-220 ℃ reactions of controlled temperature 5 hours, the gained polyol blends darkens, and the not dissolving fully of urethane solid particulate; 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 disaggregation of waste and old urethane regeneration polyvalent alcohol; It is characterized in that: comprise forcing machine (1), even matter jar (2) and segmentation microwave reactor (3), wherein said forcing machine (1), even matter jar (2) are connected with segmentation microwave reactor (3) successively; Segmentation microwave reactor (3) comprises the processing leading portion (31) that contains microwave generator separately and handles back segment (32) that the junction of handling leading portion (31) and processing back segment (32) is provided with treatment agent inlet (33).
2. continuous production device as claimed in claim 1 is characterized in that also comprising pump (4), and even matter jar (2) is connected with segmentation microwave reactor (3) through pump (4).
3. continuous production device as claimed in claim 1 is characterized in that said forcing machine (1) is a twin screw extruder.
4. continuous production device as claimed in claim 1; The processing leading portion (31) that it is characterized in that said segmentation microwave reactor (3) comprises first heating chamber (301) that is equipped with first microwave generator (311) and first shielding unit (321); Handle back segment (32) and comprise second heating chamber (302) that is equipped with second microwave generator (312) and secondary shielding device (322); First heating chamber (301) and second heating chamber (302) are separated by first shielding unit (321) and secondary shielding device (322), and treatment agent inlet (33) is arranged between first heating chamber (301) and second heating chamber (302).
5. the continuous production method of disaggregation of waste and old urethane regeneration polyvalent alcohol is characterized in that using in the claim 1 ~ 4 each described continuous production device and carries out according to the following steps:
(1) waste polyurethane is added forcing machine, forcing machine is preheated to 220 ℃ in advance;
(2) in forcing machine, add the alcoholysis agent of inhibitor, catalyzer and 40 ~ 60%;
(3) get into even matter jar from the effusive thick work in-process of forcing machine, add remaining alcoholysis agent, in even matter jar, stir;
(4) material that will spare in the matter jar pumps in the segmentation microwave reactor, adds treatment agent, the control flow velocity, and making the time of material from the import of segmentation microwave reactor to the outlet of segmentation microwave reactor is 10-20 minute;
(5) the 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 the material that will spare in the matter jar with pump in the step (4) pumps in the segmentation microwave reactor.
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 the 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 the segmentation microwave reactor is 190-230 ℃, and the temperature of reaction of handling back segment is 80-150 ℃.
9. continuous production method as claimed in claim 5, it is characterized in that by weight proportioning be: 100 parts of waste polyurethanes, alcoholysis agent 40-200 part, catalyzer 0.03-5 part, inhibitor 0.03-3 part, treatment agent 3-80 part.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN109320764A (en) * | 2018-09-14 | 2019-02-12 | 烟台正海合泰科技股份有限公司 | It is a kind of to industrialize pure PU foam alcoholysis recovery method and Special back receipts feeding device |
| WO2023182664A1 (en) * | 2022-03-23 | 2023-09-28 | 주식회사 엘지화학 | Method for preparing recycled abs resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| CN109320764A (en) * | 2018-09-14 | 2019-02-12 | 烟台正海合泰科技股份有限公司 | It is a kind of to industrialize pure PU foam alcoholysis recovery method and Special back receipts feeding device |
| 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 |
| WO2023182664A1 (en) * | 2022-03-23 | 2023-09-28 | 주식회사 엘지화학 | Method for preparing recycled abs resin |
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| CN102618010B (en) | 2014-01-15 |
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