The refri gerati on and ai r condi ti oni ng i ndustry i s adjust-
i ng to the uni que features of new refri gerants and l ubri -
cants that are evol vi ng as a resul t of the phasi ng out of CFC and HCFC refri gerants. The new l ong term refri ger- ant repl acements to date consi st of pure components and bl ends of HFCs. The HFCs are not mi sci bl e wi th the com- monl y used mi neral oi l s thus l eadi ng to the i ntroducti on of pol yol ester l ubri cants to refri gerati on and ai r condi ti oni ng systems. The HFC refri gerants and pol yol ester oi l s requi re speci al consi derati ons wi th regard to fi l ter-dri er materi al compati bi l i ty. Regardl ess of the refri gerant and l ubri cant type, the pri - mary qual i ti es desi red i n a fi l ter-dri er are: fi l trati on, removal of moi sture, and removal of aci d. Mol ecul ar si eve i s a desi ccant that has been used for the pri mary purpose of removi ng moi sture, and acti vated al umi na pri mari l y for the purpose of removi ng aci d. I t fol l ows, therefore, that these two desi ccants be tested for compati bi l i ty wi th HFC refri gerants and pol yol ester oi l s. Compati bi l i ty i s mea- sured by degree of refri gerant decomposi ti on and i t must be noted that al l commonl y used CFCs and HCFCs (i .e., R-12, R-22, and R-502) decompose to a certai n extent i n the presence of these desi ccants. Extensi ve l aboratory testi ng and many years of posi ti ve fi el d experi ence have proven the decomposi ti on of the CFCs and HCFCs i n refri g era- ti on systems to be i nsi gni fi cant. Seal ed tube tests have shown decomposi ti on i n the presence of desi ccants i s hi gh- est wi th R-22; therefore, i ts compati bi l i ty test resul ts can be consi dered acceptabl e and used as a compari son i n the anal ysi s of a new HFC. Desi ccants are presented i n a fi l ter-dri er i n two basi c for- mats: a mol ded core and as l oose beads. The mol ded core consi sts of acti vated al umi na and mol ecul ar si eve (and pos- si bl y acti vated carbon) i n a granul ar form bound together i n a sol i d core. Loose fi l l type fi l ter-dri ers consi st of the same desi ccants i n the form of l arger beads but whi ch are not bound together. The compati bi l i ty or stabi l i ty of a gi ven desi ccant i s di fferent i n a mol ded core than i t i s i n a l oose bead format. A mi xture of acti vated al umi na and mol ecul ar si eve has proven through the years to be the most effecti ve way of keepi ng contami nati on to a mi ni mum. Compati bi l i ty of these desi ccants wi th refri gerants i s determi ned usi ng a seal ed tube test. The refri gerant i s anal yzed for decompo- si ti on. The degree of decomposi ti on determi nes i f the des- i ccant i s compati bl e wi th the refri gerant. However, as pre- vi ousl y stated, al l chl ori nated and fl uori nated carbons (CFCs, HCFCs, HFCs) decompose to a certai n degree i n the seal ed tube test, so the deci si on must be based on com- pari sons -not absol utes. I n seal ed tube tests HFC refri ger- ants have been shown to be much more stabl e than CFCs and HCFCs. Pol yol ester l ubri cants are very hygroscopi c, meani ng they have a str ong attr acti on to water . Pol yol ester oi l that i s contami nated wi th water can hydrol yze (react wi th water) to form a carboxyl i c aci d. Carboxyl i c aci ds are organi c aci ds whi ch can damage a system i f they are not removed. Extensi ve testi ng has been performed by Sporl an Val ve Company and an i ndependent testi ng l aboratory to deter- mi ne the compati bi l i ti es of mol ecul ar si eve and acti vated al umi na wi th the HFC refri gerants and the pol yol ester l ubri cants. Sporl an has al so been i nvol ved i n many fi el d tri al s wi th HFC refri gerants to determi ne the performance of the Catch-Al l on actual systems. Compati bi l i ty testi ng of desi ccant mater i al s i s done using the ANSI /ASHRAE Standard Sealed Tube Method 97-1989. The seal ed tube test i s an accepted method to determi ne compati bi l i ty of materi al s i n a refri gerati on sys- tem. The test consi sts of copper, al umi num, and steel coupons, 1.0 cc of refri gerant, 1.0 cc of the appropri ate oi l , and .50g of the subject desi ccant or core materi al s com- bi ned i n a seal ed gl ass tube. The tubes are aged for 30 days at an el evated temperature of 300F. At the end of the test peri od the tubes are tested for Cl - (chl ori de) and F - (fl uo- ri de) i on content, whi ch i ndi cates the degree of refri gerant decomposi ti on. The fol l owi ng chart summari zes the resul ts of the seal ed tube tests. The tests were performed wi th R-22 to establ i sh an acceptabl e decomposi ti on percentage and to determi ne a basel i ne. The resul ts are compared to those wi th R- 134a. The 3A mol ecul ar si eve and 4A mol ecul ar si eve resul ts are averaged val ues from three separate manufacturers mol e- cul ar si eves. Figure 1 SEALED TUBE TEST RESULTS R-22 and R-134a With Various Desiccants D ESICCANT COMPATIBILITY 7 0 1 2 3 4 5 6 Core R-22 3A MS bead R-134a 4A MS bead R-134a 3A MS bead R-22 4A MS bead R-22 Activated Alumina bead R-22 Core R-134a %
R e f r i g e r a n t
D e c o m p o s i t i o n
b y
I o n
P r e s e n t Form 40-130 February 1994 CL - F - Fi gure 1 i ndi cates that seal ed tube test resul ts i n the range of 6% to 7% refri gerant decomposi ti on are enti rel y accept- abl e and present no probl em i n actual systems. I t must be understood that the seal ed tube test i s an extremel y severe test and i s a compari son test onl y. The tubes are exposed to very hi gh temperatures i n order to accel erate the reac- ti ons. The degree to whi ch the decomposi ti on reacti ons are accel erated wi th temperature i ncrease i s i l l ustrated i n Fi gure 2. Figure 2 EFFECT OF TEMPERATURE ON SEALED TUBE TEST Molded Core/R-22/Mineral oil/Cu-AI-Fe The drasti c i ncrease i n the decomposi ti on rate as the tem- perature i ncreases shows the severi ty of the seal ed tube test. At the temperatures typi cal l y seen by a fi l ter-dri er i n a system the decomposi ti on rate i s greatl y reduced. The resul ts for the i ndi vi dual beaded desi ccants used i n l oose fi l l type fi l ter-dri ers are gi ven i n Fi gures 3 and 4. Mol ecul ar si eve was tested from three separate manufac- turers usi ng both 3 angstrom (3A) and 4 angstrom (4A) mol ecul ar si eves. The terms 3A and 4A refer to the si ze of the pore openi ng of the mol ecul ar si eve. 3A and 4A mol ecul ar si eve have the same basi c crystal structure. The actual si ze of the openi ng i s determi ned by the cati on used i n the crystal . I n a 4A si eve the cati on i s sodi um and i n a 3A si eve i t i s potassi um. The bi nders used i n the manufacturi ng of the mol ecul ar si eves affect the si eves compati bi l i ty and water capaci ty. These resul ts show the greater stabi l i ty of R-134a over R-22 and the i nsi gni fi cant di fference wi th R-134a between usi ng 3A and 4A mol ecul ar si eve. R-22 gi ves decomposi ti on rates i n the range of 6% to 7% wi th 4A si eve and 1% wi th 3A si eve. R-134a gi ves decomposi ti on rates i n the range of.01% wi th 4A si eve and .005% wi th 3A si eve. Figure 3 SEALED TUBE TEST RESULTS Beaded Molecular Sieves R-22/Mineral oil/Desiccant/Cu-AI-Fe Figure 4 SEALED TUBE TEST RESULTS Beaded Molecular Sieves R-134a/Polyolester oil/Desiccant/Cu-AI-Fe Page 2 / Form 40-130 8 CL - F - 4A 3A 0 1 2 3 4 5 6 7 4A 3A 4A 3A Supplier A Supplier B Supplier C 4A 3A 0.02 4A 3A 4A 3A Supplier A Supplier B Supplier C 0 0.005 0.01 0.015 %
R e f r i g e r a n t
D e c o m p o s i t i o n
b y
F -
P r e s e n t %
R e f r i g e r a n t
D e c o m p o s i t i o n
b y
I o n P r e s e n t CELCIUS FAHRENHEIT 100 212 150 302 125 257 3.0 2.0 1.0 0.5 %
R - 2 2
R E A C T E D ACTUAL FIELD TEST RESULTS I n order to prove the effecti veness of the Catch-Al l i n HFC/pol yol ester l ubri cant systems, Sporl an has parti ci pated i n several fi el d tri al s. One wi del y documented tri al was spon- sor ed by the New Yor k State Ener gy Resear ch and Devel opment Authori ty and the Empi re State El ectri c Ener gy Resear ch Cor por ati on. The tr i al featur ed the Hannaford Brothers Shop 'n Save supermarket i n Gl ens Fal l s, New York. At thi s store R-134a and pol yol ester l ubri - cant have been used i n medi um temperature and ai r condi - ti oni ng systems. Sporl an Catch-Al l s were used throughout and the contami nant l evel s were cl osel y moni tored. Fi gur e 5 pl ots the moi stur e content and Fi gur e 6 the aci d number of the pol yol ester oi l ver sus ti me on the medi u m temper atu r e r efr i ger ati on s y s tem. Both Figure 5 GLENS FALLS SHOP N SAVE DEMONSTRATION RESULTS Oil Analysis for Med-Temp Rack With POE Oil CONCLUSION Whi l e the testi ng di scussed to thi s poi nt was performed wi th R-134a, many other al ternati ve refri gerants have been tested for compati bi l i ty wi th Sporl an mol ded cores. The seal ed tube tests and fi el d tri al s have shown si mi l ar resul ts. Seal ed tube test resul ts for several al ternati ve refri gerants are shown i n Fi gure 7. The conclusion to be drawn from the test results and field tests is that the Sporlan Catch-AII, which has proven superior performance for many years, continues to be the proper choice for alternative refrigerants. pl ots show a general decrease i n moi sture content and aci d number of the oi l . The fi nal val ues after 50 weeks show a moi sture content of 45 ppm and an aci d number of 0.04. The ai r condi ti oni ng system showed si mi l ar trends wi th fi nal resul ts of 70 ppm water and an aci d number of 0.03. The resul ts of the oi l anal ysi s l ed to the concl usi on by Aspen Systems, I nc. (an engi neeri ng research fi rm) that Sporl an Catch-Al l s can mai ntai n moi sture l evel s bel ow 50 ppm on the R-134a and pol yol ester system. Wear anal ysi s of two compressors found wear patterns si mi l ar to those found on compressors runni ng wi th tradi ti onal refri ger- ants and l ubri cants. Duri ng the test peri od there were no moi sture or l ubri cant rel ated probl ems. Figure 6 GLENS FALLS SHOP N SAVE DEMONSTRATION RESULTS Oil Analysis for Med-Temp Rack With POE Oil Figure 7 SEALED TUBE TEST RESULTS OF THE CATCH-ALL WITH ALTERNATIVE REFRIGERANTS Form 40-130 / Page 3 COURTESY OF HANNAFORD BROS. PORTLAND, MAINE RESEARCH CONDUCTED BY ASPEN SYSTEMS MARLBOROUGH, MASS. 250 M o i s t u r e
( p p m ) Weeks 60 40 20 0 0 50 100 150 200 Increases in water concentration are due to opening of the system 0.15 A c i d
N u m b e r Weeks 60 40 20 0 0 0.05 0.10 2 R-402A (HP-80) R-404A (HP-62) R-401A (MP-39) R-134a R-125 R-123 0 0.5 1 1.5 Cl - %
XXIVth International Congress of Pure and Applied Chemistry: Plenary and Main Section Lectures Presented at Hamburg, Federal Republic of Germany, 2–8 September 1973