Layman's report LIFE ENV/D/000398 "Large scale polyurethane recycling"

List o !ey "or#s an# a$$re%iations

APPs

aromatic polyester polyols (often used in the manufacture of insulation materials) Deutsche Gesellschaft fr KunststoffRecycling mb (German company dealing !ith the recycling of plastics) Duales "ystem Deutschland (German !aste disposal system) Recycling plant !ith a capacity of $ tonnes Registered brand name of recycling-polyols produced by RA&P' Registered brand name of P(Rproduced by RA&P'

DKR

D"D R#A $%%% Recypol

Recypur "ystems Petol

)rand name of aromatic polyester-polyols manufactured by RA&P' from post-consumer P*+ Polyethylenterephthalate, a plastic from !hich soft-drin- bottles and pac-aging are mostly manufactured no!adays

P*+

&ontents list

Project goals...........................................................................................................................4 Polyurethane recycling ........................................................................................................ 4 Large-scale polyurethane recycling..................................................................................... 5 Description of the process.....................................................................................................6 Description of the plant........................................................................................................ 7 Details of the plant................................................................................................................ 7 Products................................................................................................................................. 9 PUR- yste!s....................................................................................................................... "# Results.................................................................................................................................. "" u!!ary.............................................................................................................................. "$ % &ord of than's................................................................................................................. "4

'ro(ect goals
+he o.erall goal of the /0'* Pro1ect !as to demonstrate a real economically and ecologically .iable recycling (cycle) of all polyurethane plastics (P(R) and then to effecti.ely implement it2 &ore than 324 million tonnes of P(R are produced annually in the *( !hich are recycled either directly or only partially after ha.ing been used, other!ise they are incinerated2 0t is possible to recycle all P(R !aste5 to sa.e resources and also to a.oid5 to a large e6tent5 both !aste products and the liberation of #73 through the !idespread use of large-scale demonstration plants and ne! processes2 A further area of application5 !hich became apparent during the course of the pro1ect5 is the recycling of post-consumer P*+ !aste in the large-scale recycling plant !hich came into being during the pro1ect2 +he final product of this is a high 8uality aromatic polyester-polyol !hich is e6ceptionally !ell suited to the production of insulation foams2

'olyurethane recycling
Polyurethane (P(R) is produced from a basic li8uid materials5 polyol (A-components) and isocyanate ()-components)2 After the t!o components ha.e been mi6ed (in .arious proportions)5 hardening spontaneously begins follo!ed by cross-lin-ing gi.ing rise to P(R-polymer2 )y adding .arious reagents5 numerous P(R foams !ith .arious properties can be produced2 +he plastic5 polyurethane5 in the form of fle6ible foams (mattresses5 seats)5 insulation foams5 integral foams (car parts5 shoe soles) and compact elastomeres (coatings) has become an indispensable part of our e.eryday li.es2 0n fact5 about $9 of the total !orld consumption of plastics is for polyurethane2 +he consumption in :estern *urope !as 324 million tonnes in ;<<< and $=45%%% tonnes in Germany, there is an up!ard trend> ?o!5 although plastics of the thermoplastic type5 such as polypropylene5 polyethylene5 P*+ or P@# can be recycled simply by melting them do!n5 the possibilities of recycling P(R foams ha.e up to no! been limited5 due to their duroplastic nature2 ence5 P(R had long been thought to be non-recyclable or that it !as .ery comple6 to recycle2 :ith greater attention being gi.en to the en.ironment5 the ecological re8uirements of materials are also becoming more stringent2 "o5 in order not to restrict the use of the plastic P(R due to inade8uate recyclability5 research on numerous processes !as carried out5 so as to also be able to recycle this duroplastic type of plastic2 0n addition to the less en.ironmentally friendly processes for the reco.ery of energy5 se.eral mechanical processes for the reuse of P(R ha.e come into being2 :hereas only a small portion of the energy used for manufacturing is retrie.ed in the form of heat during the energy-reco.ery process5 in the case of material recycling5 at least the recyclate is reintegrated into the original production2 ?e.ertheless5 e.en !ith the best process5 the so-called regrind method by !hich e6tremely finely ground P(R po!der is added to the polyol components5 only about ;%9 of the recyclate can be added due to the increased .iscosity2

ence it is the only recycling process !hich is !orthy of the name chemical recycling2 0t has no disad.antages and is the only process !hich offers the possibility of producing high-8uality polyurethane products from ;%%9 recycled polyols2

Large)scale polyurethane recycling

Glycolosis has long been -no!n as a process for the chemical reco.ery of rigid and integral foams2 RA&P' *cosystems has5 in cooperation !ith ' Aalen and !ith the support of the *( /0'*-Programme5 de.eloped three ne! types of processes (partial glycolosis5 polyolysis5 acidolysis) and has also used them for the first time technically on a large scale for the reco.ery of ra! materials5 including semi-rigid and fle6ible P(R foams2 +he processes !ere pre.iously only used in small laboratory and technical applications2 RA&P' *cosystems Gmb A #o2 KG has no! managed to incorporate all the abo.e-mentioned recycling processes in a recycling plant specially create# $y *+,'F Ecosystems !hich has made industrial applications possible-

'ig2 ;B R#A $%%%

Description o the process

P(R !aste is bro-en do!n into small pieces of about $ cm in a slicer for the production of recycling polyols2 +hese are continuously introduced into a depressurised reaction container5 in !hich there are already process reagents as basic substances depending on the type of residual substances5 namely polyol5 glycol or carbo6ylic acid5 as !ell as catalysts and deaminating agents2 At temperatures of about 3%% degrees centigrade and !ith constant stirring5 the P(R molecular chains are split2 After the completion of the reaction process (lasting about C hours)5 the resultant li8uid5 !hich is a mi6ture of polyols and lo!-molecule urethane5 is filtered2 'iltration residues consist e6clusi.ely of incidental foreign matter2 +hese can easily be remo.ed through incineration !ith no after-effects and resultant energy may be reused2'inally the recycling polyol !hich has been produced is either put into storage tan-s5 0)#-containers or barrels5 as re8uested by the customer2 +he final product5 !hich is a high-8uality recycling polyol (R*#DP7/E)5 may be used either alone or mi6ed !ith ne! polyol for the production of P(R-foams2 As polyurethanes are only partially decomposed by using basic components of polyols5 the former product properties are preser.ed by cross-lin-ing !ith isocyanate2

Fig. 2: The RAMPF-process principle

0n future5 about <C - <<9 of .arious types of resultant P(R can be recycled through the efficient use of these inno.ati.e methods2 +his is particularly significant in the field of fle6ible foams !hich are by far the most important !ith regard to the 8uantities manufactured and the !aste load for !hich there has been no recycling up to no!2

Description o the plant

+he industrial plant de.eloped by RA&P' *cosystems essentially consists of three componentsB +he temperature e8ualisation unit +he materials-handling technology unit +he reactor unit &a6imum attention !as gi.en to fle6ibility and automation at the stage !hen the siFe and conception of the plant parts !ere being decided +he result is a recycling plant !hich is able to recycle residual P(R substances regardless of their shape at the time of deli.ery2 It is the irst reprocessing plant o its !in# in the "orl# or '.* recycling/ "hich can $e implemente# on an in#ustrial scale in all the pre%iously !no"n chemical recycling processes or '.*-

Abb. 3: RCA 5000

Details o the plant

+he temperature e8ualisation unitB
+he temperature e8ualisation unit consists of a gas burner utilising thermal oil as a heat transfer medium2

At e.ery possible site5 there are interfaces to ensure the future e6pansion possibilities of the plant and the inclusion of energy)sa%ing measuresA heat accumulator has already been installed2 0t ser.es as a buffer !hich can store the hot thermal oil during the cooling process and in this !ay can again ser.e as a heating medium during the ne6t production application5 !ithout necessitating a further large e6penditure of energy2 A burner has been housed in a container on its o!n5 close to the production halls as protection against fire5 The materials-handling technology unit: "tringent re8uirements !ere placed on the materials-handling technology in order to gi.e the ma6imum number of P(R producers the possibility of recycling their residual substances2 +he materials-handling technology unit enables RA&P' *cosystems to handle residual substances ha.ing different po!der densities at the rate of about ;2$ tonnesGhour2 Rampf *cosystems de.eloped a concept consisting of t!o materialshandling units5 so as to be able to satisfy such e6tremes of transportation !ithin the system2 7

The reactor unit: +he reactor is a impellent-type mi6er measuring 4mH in .olume surrounded by halfpipe coil 1ac-ets filled !ith thermal oil for temperature e8ualisation2 +he stirring de.ice I specially de.eloped to match the specifications of RA&P' *cosystems I is used to homogeneously set the temperature as !ell as to mi6 the sample !ith the residual substances2 +he plant is endo!ed !ith .arious pumps !hich introduce reagents by fully automatic means in .arious 8uantities into the reactor2 *6haust air !hich does not contain pollutants from this recycling method is separated from the condensate by passing o.er a glass cooler2 +his re-enters the reactor and is then allo!ed to enter the atmosphere after passing o.er an additional acti.e carbon filter2 After completely con.erting the residual P(R substances into a recycling-polyol5 they are then put into .arious pac-ing drums2 +o this end5 the recycling-polyol5 !hich has no! cooled to about J%K#5 passes through a filtration path !ith t!o self-cleaning lateral dis- filters of different nominal !idths at its core2 )y using the feed duct designed by RA&P' *cosystems5 it is possible to put recycling polyol into either 3%% l barrels5 0)# container or storage tan-s5 as desired2 +he entire recycling plant is controlled and monitored by a "iemens "P" control system !hich !as specifically programmed for that purpose by RA&P' *cosystems specifications2 'urthermore5 all necessary data concerning the process can be documented by this control system2 +he usefulness of this au6iliary function is not to be underestimated !ith regard to 8uality control2

Fig.4: SPS-Control RCA 5000

'ro#ucts *ecypol
+he Recycling-polyol (RecypolE) !hich has been produced during the recycling process is to be considered to be a basic polyol2 Almost all forms of polyurethane can be industrially recycled in the plant !hich has been created for this5 due to the processes !hich ha.e been specially de.eloped during the pro1ect2 All recycling processes ha.e been tailor-made for the customers and hence the resultant Recypol is created to satisfy the e6act re8uirements of a particular customer2 Recypols are particularly !ell suited for selling to customers !ho create their o!n formulae or for that matter to system-.endors that are in a position to raise these recycling-polyols to the le.el at !hich these become systems2
Fig. 5: Recypol

Fig. 6: Glycolysis

*ecypur
An additional aim of the pro1ect5 Lindustrial polyurethane recyclingL5 foresa! the possibility for P(R producers5 !ho only deal !ith ready-to-use systems5 thus being able to recycle their residual material and thereby reintegrate them as polyols in the current production2 ence5 only as a result of specific formulation in.ol.ing the addition of cross-lin-ing agents5 e6tenders5 catalysts5 stabilisers and propellants is it be possible for specifications to be achie.ed2 :ithin the scope of our o!n foam-production5 ne! P(R systems ha.e been and are also currently being manufactured on the basis of recycling polyols and sold under the brand name of Recypur2 9

Recycling polyols5 are based on P(R residual materials and hence already contain stabilisers and catalysts2 +he follo!ing formulation is hence less comple6 and also less e6pensi.e2 "ince recycling polyols are in fact high-grade5 li8uid polyols5 not only can these be added in small 8uantities to the system-polyol5 but they can in fact be used ;%%9 as the main polyol2 :hen using recycling polyols5 no additional in.estments are re8uired5 nor is a refitting of machines re8uired by someone using P(R2

'.*)0ystems
"ome P(R systems !hich !ere produced !ithin the frame!or- of the *( /0'* pro1ect on the basis of Recypol5 ha.e been presented in e6cerpts2 RA&P' *cosystems carried out the recycling of integral rigid foam residual products on demand most successfully2 0n this !ay5 ra! materials from the production of casings and !indo!-frames can be successfully reintegrated into the original manufacturing process in the form of recycling polyol2 Ad.antages in using the product become apparent5 the surface properties of moulds are better2 ?umerous ne! processes !ere de.eloped in the area of semi-rigid P(R foams2 0n this conte6t5 residual substances from production !ere used5 including the manufacture of shoe soles5 arm rests and barrel casings2 0t !as also possible to manufacture P(R systems !ith up to 4%9 of recycling-polyol2

Fig. : !ntegrals"in parts

with up to 62% Rec pol

Foaming 'arameters (i)ing Ratio "## * "+, -el .i!e +# s Rising .i!e 6# s /ree Rise Density "7# g0l

'olyol Formulation Recypol: 6+;# 7 <irgin Polyol %dditi=es >ater $4;5 7 +;5 7 ";# 7

'hysical 'roperties Density 1ardness 2 hore D3 .ensile strength 5longation at 6rea' .ensile !odulus 1ead 9 %- 9 .est
Ta#.$: rigid integral system mit 62% Recypol &'ource: R(hl-Puromer)

7## g0l 64 +# 40!! "$ 7 "6$ 40!!8 4 !!

10

0n the field of semi rigid foams a lot of ne! processes !ere de.elopped by RA&P' *cosystems during the pro1ect2 +he !aste !as ta-en out of shoe sole 5 arm rests5 automoti.e spoilers and beer -eg productions2 0t !as possible to create P(Rblendings !ith 4% 9 of such a Recypol in it2 +hey ha.e sho!n no 8uality loses against the original systems

Fig. *: semi rigid integral Recypol

+oams ,ith up to 6-%

'hysical 'roperties

*ecypol1

*2200

6est 7 *esults 8riginal ) 0ystem 3,8 473 8,7 57 100,000

6est ) ,etho#

3204 *ecypol15 Tensile strength [N/mm] El ng!ti n !t "re!# [$] Te!ring strength [N/mm] %!r&ness ['h re (] )le*i"ilit+ 5,2 464 10,1 57 100,000

DIN 53504 DIN 53504 DIN 53507 DIN 53505 DIN 53543

Ta#.2: physical properties o+ a semi rigid integral system ,ith 6-% Recypol

*esults
1, +he 8uality of post-consumer residues of fle6ible foams from old automobiles and refrigeration parts is still too lo!2 "een from a purely technical point of .ie!5 +he production of polyols using fle6ible foam !aste from shredder residue is absolutely feasible2 (so-called L"hredderleichtfra-tionL)2 +he inade8uate purity of residues (at the present time) ne.ertheless results in an economically non.iable polyol (as there is no mar-et for it)2 Post-consumer P*+ from the D"DDuales "ystem Deutschland (German !aste disposal system) is a.ailable in ade8uate 8uantities and 8uality2 +he success of P*+-recycling as !ell as the production of aromatic polyester polyols has led to the creation of a cooperation Mgly-olysis from P*+22N !ith the DKR - Deutsche Gesellschaft fr KunststoffRecycling (German company dealing !ith the recycling of plastics)2 Appro6imately $% tonnes of petol ha.e5 till no!5 been produced annually2

11

32 0n the field of systems formulation5 a ne! ready-to-use5 !ater-propelled5 fireprotected rigid foam systems !ere de.eloped5 containing up to <%9 recyclingpolyol2 +hese types of systems are needed in the entire field of construction and insulation2 A ne!ly de.eloped integral rigid foam system from 4%9 recycling polyol can be used for the manufacture of casings and !indo! frames2 0n addition5 our system-polyol R4H%% #"; has been impro.ed and has already been used as a standard product by customers (3% tonnes by %; Ouly 3%%H)2 0n 3%%= se.eral e6periments on foam !ere successfully carried out in an *( neighbouring country5 Poland5 in the field of insulation foams2 3, )y participating in the !orld-reno!ned polyurethane trade fair (+*# 3%%H in +he ague5 the results became -no!n internationally2 Dra!ing attention to it at the Polyurethane :orld #ongress5 participation in the Krauss &affai ausmesse (Krauss &affai company fair) in &unich5 our o!n recycling seminar at the Kunststoff-Pentrum /eipFig (K(P)5 namely the German plastics centre in the #ity of /eipFig5 as !ell as the technical presentation at the P(R- conference in eidelberg for trade specialists Fig. .: /tech 2--0 (P(R-'achtagung) completed the process of ma-ing the results -no!n in 3%%H2 'urther highlights concerning .arious e.ents at !hich the results !ere publicised included the participation at the plastics fair in 3%%= in Dsseldorf5 a presentation at the 'raunhofer 0nstituts in Krefeld in Krefeld in "eptember 3%%= at the ;Hth Plastics and Recycling #ollo8uim as !ell as participation in a panel discussion at the ?iedersQchsischen Kunststofftag (Plastics #on.ention of /o!er "a6ony) in )raunsch!eig2 ence5 the results ha.e successfully been made -no!n in the *( and in the !orld at large and chemical recycling can5 on the strength of these positi.e trends5 no! effecti.ely implement the .arious tas-s2 =2 :ithin the frame!or- of the pro1ect5 numerous recycling formulations !ere produced for .arious polyurethane substances2 +he first formulation !as successfully used on the ne! $ tonne plant after only a fe! months and this in.ol.ed the recycling of compact P(R2 +o date5 some H%% tonnes of a recycling polyol ha.e been produced from compact P(R2 0ntegral foam from !indo! frames and semi-rigid integral foam from shoe-sole production !ere also successfully con.erted to recycling polyols on the R#A $%%% (about $% tonnes per annum)

12

0ummary
(nder normal conditions of production5 $ - ;%9 of the P(R are residual substances from !ithin the plant2 +his in turn means that for any one company5 these residual materials represent an increase in costs (such as disposal fees of some ;%% - 3%% RGtonne) as !ell as %alua$le ra" materials "hich are "aste#2 +here is clearly a real necessity for ra! materials to be reintegrated into the production cycle5 i2e2 the reutili9ation o ra" materials+he declared aim of RA&P' *cosystems are therefore the sa%ing o %alua$le ra" materials and #ecreasing the $ur#en put on "aste #isposal #umps !hilst at the same time decreasing costs and re#ucing "aste #isposal e:penses2 +herefore5 by reusing P(R5 the ecological and economic factors are once again being brought into harmony22 :ith the help of the recycling plant !hich has been supported by the *( /0'*Programme and de.eloped by RA&P' *cosystems5 all P(R producers !ere5 for the first time5 gi.en the possibility of reintegrating their residual substances into the production in the form of a recycling-polyol2 0t is furthermore possible to recycle the large 8uantities of Lpost-consumerL !aste5 such as P*+ bottles5 pro.ided that the necessary purity of the post-consumer residues still permit a recypol to be mar-etable2 +he use of recycling-polyol offers special ad.antages to the userB Preser.ation of former product characteristics by means of cross-lin-ing *asy integration into the production cycle !ithout the necessity of retrofitting machines Adding the recyclate to the ne! product !ithout a loss in 8uality of the final product 7b.ious cost-sa.ing !ith regard to the primary polyol ;004 reintegration o the "aste materials "a.ing on disposal fees by re-processing the residual P(R-substances Possible compliance !ith the legal ordinances5 regulations and conditions (+A"iGGerman :aste Disposal 7rdinance) 0mage boost through impro.ed en.ironmental balance sheets +he reprocessing plant de.eloped by RA&P' *cosystems enables the P(R processing industry the possibility of recycling P(R5 something !hich has hardly been done till no!2 +his ma-es the recycling of P(R on a large scale possible, the immediate conse8uence of !hich is the a.oidance of P(R-!aste5 preser.ing resources and the a.oiding #732 +he result is an .ery significant relief for the en.ironment2

+ "or# o than!s
A !ord of than-s is e6tended to all those !ho lent their support for this pro1ect !ithin the frame!or- of the *( /0'*-Programmes2 13