CN101381475B - Dechlorination and defluorination processing method of polyurethane rigid foam - Google Patents

Dechlorination and defluorination processing method of polyurethane rigid foam Download PDF

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CN101381475B
CN101381475B CN2008101717266A CN200810171726A CN101381475B CN 101381475 B CN101381475 B CN 101381475B CN 2008101717266 A CN2008101717266 A CN 2008101717266A CN 200810171726 A CN200810171726 A CN 200810171726A CN 101381475 B CN101381475 B CN 101381475B
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temperature
design temperature
hard polyurethane
polyurethane foam
foam
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CN101381475A (en
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刘景洋
郭玉文
杨勇
乔琦
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刘景洋
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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
    • 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
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • 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

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a method for dechlorinating and defluorinating a polyurethane hard bubble. The method comprises the following steps: crushing the polyurethane hard bubble into a particle shape in a closed container; heating and insulating the closed container at the set temperature of between 100 and 170 DEG C,for 1 to 10 hours after the temperature rises to the set temperature; replacing gas in the closed container; reclaiming a foaming agent in the replaced gas; and putting the gas which recyclaims the foaming agent into air space via activated carbon filtration. The method has the advantages that the foaming agent packed in holes of the polyurethane hard bubble and absorbed in foaming particle solid is removed and collected, the removing rate is improved from between 60 and 70 percent to over 96 percent so as to further reduce severe harm to environment and human body of sal ammoniac, chlorobenzene and chlorophenol formed by Cl element from CFC-11 generated by burning, and benzene, phenol and ammonia generated by high-temperature burning, thereby reducing the greenhouse effect caused by total discharge of CFC-11.

Description

A kind of dechlorination and defluorination processing method of polyurethane rigid foam
Technical field
The invention belongs to the environmental technology field of waste and old material recycling, a kind of dechlorination and defluorination processing method of polyurethane rigid foam of particularly a kind of lagging material that is widely used in building, refrigerator, refrigerator-freezer and the refrigerated shipment---hard polyurethane foam; This method comprises: described hard polyurethane foam is carried out break process, adds gentle insulation processing, gas displacement processing, condensation recycling, filtration treatment.
Background technology
The material of a lot of chloride halocarbons that causes Global warming and depletion of the ozone layer is as being used as the whipping agent in the household electrical appliance lagging material, for example refrigerator and refrigerator-freezer.After finishing, its life cycle all needs these are carried out break process with regard to household electrical appliances.The whipping agent of scrapping at present in the household electrical appliances lagging material mostly is CFC-11, CFC-11 belongs to CFCs (fluorochlorohydrocarbon class material), find that after deliberation nearly 1/4 whipping agent CFC-11 is adsorbed in the lagging material solid, only can discharge the whipping agent that is wrapped in the abscess (account for whipping agent total amount 3/4) when broken, and absorbed portion is difficult to discharge.
Abroad mainly be to adopt incinerating method to handle lagging material at present.Consider cost issues, generally lagging material is crushed to 2～4mm size, the content of CFC-11 surpasses 1/4 of total amount in the lagging material particle of finding after deliberation to obtain after the industrial fragmentation, and the lagging material particle carries out high temperature incineration at 850～1000 ℃, primary product is HCl (hydrogenchloride), HF (hydrogen fluoride), CO2, H2O, a small amount of CO, NO, NO2, N2O, and wherein HCl and HF are mainly generated by CFC-11.HCl and HF are strongly-acid gas, and burning facility is had the deep-etching effect.When the lagging material particle burns under 850 ℃, gone out the CFC-11 (fluoro trichloromethane of lossy ozonosphere, CC13F), CFC-12 (methyl chlorofluoride, CCl2F2) and outside the CCl4 material discharges, the also CH2Cl2 of lossy ozonosphere, CH3Cl, and benzene, phenol and ammonia from Cl element among the CFC-11 and high temperature incineration generation form ammonia chloride, chlorobenzene and chlorophenol, and environment and human body are had serious harm.
Summary of the invention
The objective of the invention is a kind of dechlorination and defluorination processing method of polyurethane rigid foam technical scheme of proposing at fluorochlorohydrocarbon class material residual in the thorough removing hard polyurethane foam.
Technical scheme of the present invention is achieved in that a kind of dechlorination and defluorination processing method of polyurethane rigid foam, at first in an airtight container, hard polyurethane foam is broken into particulate state, the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 100 ℃ to 170 ℃, soaking time is to keep 1 to 10 hour after temperature rises to design temperature, then the gas that has in the hard polyurethane foam crushed particles encloses container is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent, it is direct or send into airspace through active carbon filtration to reclaim gas behind the whipping agent then.
The invention has the beneficial effects as follows: the present invention will be wrapped in the CFCs that hard polyurethane foam abscess neutralization is adsorbed in the foam beads solid and remove and collect, the rate that removes is brought up to more than 96% from 60%-70%, reduced further minimizing that produces owing to burning disposal owing to benzene, phenol and ammonia from Cl element among the CFC-11 and high temperature incineration generation form ammonia chloride, chlorobenzene and chlorophenol, environment and human body there are serious harm, and the Greenhouse effect that cause of the full release of CFC-11.
With the refrigerator is example, and China refrigerator society recoverable amount surpassed 1.5 hundred million in 2007, it is estimated that from 2003, will be eliminated every year with 4,000,000 speed.Scrap and to produce a large amount of PUR foam beads after refrigerator is handled by Mechanical Crushing, if every refrigerator is pressed the 6kgPUR frothmeter, 4,000,000 refrigerators will need 2.4 ten thousand tons of PUR foams of break process, if the foam beads after the fragmentation behind heating 4h under 160 ℃, can be reduced by 1350 tons of CFC-11 and is discharged in the atmosphere.550gCFC-11 discharges the Greenhouse effect that cause fully and equals 2200kgCO in the refrigerator PUR foam 2Burst size, calculate and to learn and be equivalent to discharge less every year 5400000 tons of CO after using the inventive method 2To the caused Greenhouse effect of atmosphere.
Below in conjunction with drawings and Examples the present invention is made a detailed description.
Description of drawings
Fig. 1 removes CFCs processing technological flow figure for hard polyurethane foam;
Fig. 2 is the graph of a relation of hard polyurethane foam mass loss and temperature;
Fig. 3 is hard polyurethane foam mass loss and time relation figure;
Fig. 4 is three kinds of gaseous sample total ion current figure (TIC figure) of low-temperature heat;
Fig. 5 is ten kinds of gaseous sample TIC figure of low temperature pyrogenation.
Embodiment
Embodiment 1
Fig. 1 removes fluorochlorohydrocarbon class material technological process embodiment for hard polyurethane foam, at first in an airtight container 1, utilize crusher 2 that hard polyurethane foam 3 is broken into particulate state 3-1, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, promptly in airtight container, the hard polyurethane foam after the fragmentation is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 100 ℃ to 170 ℃, soaking time is according to the difference of design temperature and difference, generally be after temperature rises to design temperature, to keep 1 to 10 hour, being wrapped in the CFCs that hard polyurethane foam abscess neutralization is adsorbed in the foam beads solid this moment can be removed, the rate that removes is more than 96%, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into condensing engine 4 condensations reclaim whipping agent (CFC/HCFC) to whipping agent withdrawing can 5, this recovery technology is a kind of known technology, condensing temperature is the liquid point temperature of whipping agent (CFC/HCFC), generally be below 23.8 ℃, the gas that will reclaim then behind the whipping agent directly or after filter activated carbon chamber 6 is sent into airspace.CFC-11 (CCl wherein 3F, fluoro trichloromethane), CFCs (fluorochlorohydrocarbon compounds), HCFCs (hydrogen fluorochlorohydrocarbon compounds) are different whipping agent compounds.
In the present embodiment, the described speed of heating from normal temperature to the design temperature is 5 ℃～10 ℃/minute.
In the present embodiment, the hard polyurethane foam particle of described fragmentation can be circular or irregularly shaped its particle diameter is 2mm～4mm.
Wherein in the process of removing whipping agent, the size of crushed particles and the height of design temperature directly can influence the length of temperature hold-time.
Aforesaid method also can be divided into for two steps, at first in airtight container hard polyurethane foam was carried out fragmentation, and the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, and the gas that displaces is sent into the condensing engine condensation reclaim whipping agent; Then hard polyurethane foam particle after the fragmentation is put into the hard polyurethane foam of another encloses container that can heat after and added gentle insulation fragmentation, heat and be from normal temperature to the design temperature, design temperature is between 100 ℃ to 170 ℃, soaking time is according to the difference of design temperature and difference, generally be after temperature rises to design temperature, to keep 1 to 10 hour, temperature in the airtight container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent, it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 2
Present embodiment is that hard polyurethane foam is removed the concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is at 100 ℃, soaking time is to keep 10 hours after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 3
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is at 120 ℃, soaking time is to keep 8 hours after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 4
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is at 140 ℃, soaking time is to keep 6 hours after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 5
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 155～160 ℃, soaking time is to keep 1 to 2 hour after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 6
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 155～160 ℃, soaking time is to keep 2 to 4 hours after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 7
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 160～170 ℃, soaking time is to keep 1 to 2 hour after temperature rises to design temperature, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 8
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 160～170 ℃, soaking time is to keep after temperature rises to design temperature between 2 to 4 hours, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Embodiment 9
Present embodiment is that hard polyurethane foam is removed another concrete technology that CFCs handles, referring to embodiment 1, at first in an airtight container, hard polyurethane foam is carried out fragmentation, make rigid polyurethane soak the particulate state of diameter at 2～4mm, portion C FCs can be released along with the fragmentation of hard polyurethane foam, yet CFCs that wrap up this moment in not breaking abscess and the CFCs that is adsorbed in hard polyurethane foam (PUR foam) solid also fail to discharge, therefore the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 170 ℃, soaking time is to keep after temperature rises to design temperature between 1 to 2 hour, temperature in the airtight then container is got back to normal temperature gradually, afterwards the gas that has in the hard polyurethane foam particulate encloses container of broken back is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent (CFC/HCFC), it is direct or send into airspace behind active carbon filtration to reclaim gas behind the whipping agent then.
Following examples 10 to 11 are that the hard polyurethane foam described in the embodiment 1 to embodiment 9 is removed in the concrete technology of CFCs processing, in encloses container, the heat description of detail parameters of process of particulate state hard polyurethane foam, the description of pyrolysis temperature range and mass loss parameter under the cold condition specifically, the material of use are to have typical case's representative and the intact PUR hard polyurethane foam of scrapping in the refrigerator.
Embodiment 10
At first, obtain 4mg diameter 5mm, the PUR hard polyurethane foam right cylinder of high 4mm with the cutting of PUR hard polyurethane foam, the hard polyurethane foam right cylinder is positioned in the crucible that uses thermogravimetric analyzer (PerkinElmerPyrisl TGA), carry out the experiment of six thermogravimetrics, at every turn all with the speed of 10 ℃/min since 40 ℃ of intensification, but each outlet temperature difference all, be respectively 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃ and 180 ℃, constant temperature 4h under outlet temperature respectively again then; Constant temperature carries out the thermogravimetric data determination after finishing.
By as shown in Figure 2: the cylindrical mass loss of described PUR hard polyurethane foam is respectively 1.20%, 2.16%, 4.29%, 5.63%, 7.33%, 11.01%; Obviously increase but compare mass loss with other temperature for 180 ℃, pyrolytic reaction may take place in the PUR foam in the time of 180 ℃.Absorption and the gas release amount that is wrapped in the PUR foam increase with the rising of temperature, i.e. rising along with temperature increases in the burst size of identical time same substance.
By as shown in Figure 3,160 ℃ of heating down, it is very obvious begin 1 hour PUR foamy weightlessness, and 1～2h weightlessness is obviously slowed down, and the variation of 2～4hPUR froth quality is extremely very little.
Embodiment 11
The diameter that firm fragmentation is good is packed into less than the PUR foam beads of 4mm in the encloses container, and respectively behind 100 ℃, 120 ℃, 140 ℃ and 160 ℃ of following constant temperature 4h, the container composition of gases within is CFC-12, CFC-11 and CCl4 all at each temperature, does not detect other gaseous constituents.
Shown in Fig. 4 TIC (total ion current figure), (among Fig. 4,1 is the CFC-12 peak; 2 are-the CFC-11 peak; 3 are-CCl 4The peak), the library searching matching rate of three kinds of gases is all more than 90%.Whipping agent in the PUR foam is CFC-11, but detected result shows to also have CFC-12 and CCl 4, this is main because when producing CFC-11, utilizes HF and CCl 4React, primary product is CFC-11, but also follows a small amount of CFC-12 to generate simultaneously, so can contain CFC-12 and CCl in the PUR foam 4, illustrate that the whipping agent CFC-11 purity of using is not high.
CFC-11 concentration, quality and mass percent are as shown in table 1 in 160 ℃ of following different heating time encloses containers.Behind heating 1h, 2h and the 4h, as shown in Figure 3, described PUR foam fine particle mass loss is respectively 6.15%, 7.06% and 7.33% under 160 ℃; CFC-11 that discharges as shown in Table 1 and foam beads mass percent are respectively 5.24%, 5.92% and 5.99%, can estimate at 160 ℃ down during the described PUR foam beads of heating, and CFC-11 accounts for and discharges 82～85% of gas gross.
Table 1: CFC-11 concentration, quality and mass percent in the encloses container
160 ℃ of constant temperature 1h 160 ℃ of constant temperature 2h 160 ℃ of constant temperature 4h
CFC-11 concentration in the container 23.8mg/L 26.9mg/L 27.2mg/L
Discharge the CFC-11 quality 26.2mg 29.6mg 29.95mg
Discharge CFC-11 and PUR foamy mass percent 5.24％ 5.92％ 5.99％
The gas that PUR foam fine particle produces when being heated to 180 ℃ and 200 ℃ mainly contains propylene, propine, CH 3Cl, dimethyl allene, 1-butylene, 2-butylene, CFC-11, pentane, CH 2Cl 2And CCl 4Total ion current figure (TIC) is as shown in Figure 5: the library searching matching rate of 10 kinds of gases is all more than 90%.(among Fig. 5,1 is-the propylene peak, and 2 are-the propine peak, and 3 are-CH 3The Cl peak, 4 are-the dimethyl allene peak, and 5 are-the 1-butylene peak, and 6 are-the 2-butylene peak, and 7 are-the CFC-11 peak, and 8 are-the pentane peak, and 9 are-CH 2Cl 2The peak, 10 are-CCl 4The peak; ).
Do not detect CFC-12, select ion detection to prove by GC/MS: mainly be because propylene and CFC-12 to go out the peak retention time identical, the peak of high density propylene covers the peak of lower concentration CFC-12, has CFC-12.Experimental result shows pyrolytic reaction has taken place when the PUR foam is heated to 180～200 ℃, produces in the gas and is mainly alkene, contains methyl chloride and fluorochlorohydrocarbon class material, there is no liquid oily deposits yields.
About 0.3～the 0.4mm of structure abscess mean diameter of 160 ℃ of preceding foam abscesses of heating, the quantity of breaking of heating back PUR foam abscess is than the preceding showed increased of heating.Illustrating that heating PUR foam causes that abscess breaks, is to make a kind of method that is wrapped in CFCs snap-out release in the PUR foam abscess.Along with the rising of temperature, the speed that the CFCs gas molecule passes cell wall increases.
Learn that by table 1 discharging CFC-11 is respectively 5.24%, 5.92% and 5.99% with PUR foamy mass percent, can calculate, in the removable foam beads of difference 84.5%, 95.5% and 96.6% of the CFC-11 total amount at 160 ℃ down behind heating 1h, 2h and the 4h.Behind heating 1～2h in the foam beads CFC-11 content only account for 0.28～0.96% of foam beads quality.
From the foregoing description as can be known after present method is handled, eliminated the CFC-11 that the PUR hard polyurethane foam contains, PUR hard polyurethane foam afterwards carries out burning disposal and can not produce the benzene, phenol and the ammonia that produce from the Cl element among the CFC-11 and high temperature incineration and form ammonia chloride, chlorobenzene and chlorophenol, can harm not arranged to environment and human body, and because the Greenhouse effect that the full release of CFC-11 causes.Eliminated the CFC-11 that the PUR hard polyurethane foam contains in addition, PUR hard polyurethane foam afterwards also can safe conduct be made other purpose starting material use such as cutlery box, disposable water cup.

Claims (9)

1. dechlorination and defluorination processing method of polyurethane rigid foam, it is characterized in that, at first in an airtight container, hard polyurethane foam is broken into particulate state, the encloses container that has the hard polyurethane foam crushed particles is added gentle insulation, heat and be from normal temperature to the design temperature, design temperature is between 100 ℃ to 170 ℃, soaking time is to keep 1 to 10 hour after temperature rises to design temperature, the gas that has in the hard polyurethane foam crushed particles encloses container is replaced, the gas that displaces is sent into the condensing engine condensation reclaim whipping agent, gas behind the recovery whipping agent is sent into airspace, and the described speed of heating from normal temperature to the design temperature is 5 ℃～10 ℃/minute.
2. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that the hard polyurethane foam grain diameter of described fragmentation is 2mm～4mm.
3. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is at 100 ℃, soaking time is to keep 10 hours after temperature rises to design temperature.
4. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is at 120 ℃, soaking time is to keep 8 hours after temperature rises to design temperature.
5. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is at 140 ℃, soaking time is to keep 6 hours after temperature rises to design temperature.
6. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is between 155～160 ℃, soaking time is to keep 1 to 2 hour after temperature rises to design temperature.
7. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is between 155～160 ℃, soaking time is to keep 2 to 4 hours after temperature rises to design temperature.
8. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is between 160～170 ℃, soaking time is to keep 1 to 2 hour after temperature rises to design temperature.
9. according to the described a kind of dechlorination and defluorination processing method of polyurethane rigid foam of claim 1, it is characterized in that described design temperature is between 160～170 ℃, soaking time is to keep between 2 to 4 hours after temperature rises to design temperature.
CN2008101717266A 2008-10-24 2008-10-24 Dechlorination and defluorination processing method of polyurethane rigid foam Expired - Fee Related CN101381475B (en)

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PT3744812T (en) * 2019-05-27 2022-03-24 Covestro Deutschland Ag Method for the recycling of polyurethane material waste for the production of chemical raw materials for the production of isocyanates and polyurethanes

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1132762A (en) * 1995-04-07 1996-10-09 张金炳 Reproduction of foamed polyurethane
JP2007191612A (en) * 2006-01-20 2007-08-02 Bridgestone Corp Method fir grinding polyurethane foam using microorganism
WO2007091108A1 (en) * 2006-02-08 2007-08-16 Ahd Vagyonkezelö És Tanácsadó Kft Device for decomposing pvc based and other plastic waste materials with high halogen content
WO2008022713A1 (en) * 2006-08-19 2008-02-28 Bayer Materialscience Ag Process for production of polyols and/or polyamines from polyurethanes, polyurethaneureas and polyureas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132762A (en) * 1995-04-07 1996-10-09 张金炳 Reproduction of foamed polyurethane
JP2007191612A (en) * 2006-01-20 2007-08-02 Bridgestone Corp Method fir grinding polyurethane foam using microorganism
WO2007091108A1 (en) * 2006-02-08 2007-08-16 Ahd Vagyonkezelö És Tanácsadó Kft Device for decomposing pvc based and other plastic waste materials with high halogen content
WO2008022713A1 (en) * 2006-08-19 2008-02-28 Bayer Materialscience Ag Process for production of polyols and/or polyamines from polyurethanes, polyurethaneureas and polyureas

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