Document kDLK1JKKnYZpg0zrgo2j1mB70

..r, J. I, Jt-sehor . I . *u boat de '-'psaours ?j f o * In c. Yr gisiic .'jtieuticals u iv ic io n ;iin in gtcu i* relaw are October Id , I f 3 9 Gar Joe t You may r t n ^ o b o r t h a t d u r in g ray l a s t vtd ifc in Deepw ater we d isc u sse d th e yroble.-a o f th o d i sp o sa l o f id%e--xULi^:j9\which accu m u lat es in t ar fc o a r s, I m a 't a o h it t " h e r e t o a odt,.y ^ r ?>~ec "r e p o r t LTD ,,-3345 co v e r in g t h e in v o st ir a t io x i o f th e co m p o sit io n arid r e co v e r y o f su ch a slu dge * V ' V \ r o a ih o p o in t o f r i v y / c t f t h e h ispard in v o lv e d i t i s c l e a r t h a t o t e an d i s t i l l a t i o n i s such. t o ^ / p r e fe r r p ^ l/ t o mere ditocin g o f th e slu d ge it se lf, irresp ective of the lobttion dump, jl. secon d p o in t in fav o r o f th e d i s t i l l a t i o n i s t h a K i \ , y | ^ i d s s. c e r t a in amount o f r eco v e r e d fl u i d vfrieh i s p r e t t y y o o ^ o x o c g t ;bar<a s l i g h t l y e x c e so iv e b ism u th co n t en t -.vhieii, lioiw ver , can pr.ch jibiy-f/iN cu t tNiyin by a p p r o p r ia t e ar o in g on. st o r a g e '.Veil i f t h i s i s i..p - r ^ t fio ft l, l ;\ t b Leif, .hi/' o f a sm all u n cu at o f su ch recover* :-.-d fl u i d in r o i- u lar /pro d u ct io n w tu ld n ot s i g n i f i c a n t l y r a i s e t h e bism u th content * ; '< M \\ / / ;-.ooordinn t e k o u r c a lc u la t io n s b a se d on fi g u r e s su p p lie d b y Mr* ,asr-rriiu i, c o lle c t e d in tank: c a r s t o correspon d t o O .viif biornuth on th e b a sis"o f t h e le a d , which fig u r e I u n d erstan d i s above the a'/o r ay e bissaxbh co n t e n t o f you r p ig lo a d * f.uch a s i t u a t i o n , o f c o u r se , i s bound | t o a r i s e unidir you r p r e se n t p r a c t i o e , w h ich 1 u n d er stan d i s t o dump th e steiou s t i l l rooi/iyies o f th e d i s t i l l a t i o n o f slu d ge from Et h y l flu id or t o t r a e t f t ^ l c a d r ig h # / in t o one o f you r r e g u la r slu d ge p i t s * Th is an. on ly le a d t o avjb u ild - ]^ 'A If t h e bism u th c o n t e n t o f you r le ad in p r o c e ss, t h e u l - tiesate r efiM s^ - y r 'o cess r e a lly takin g. p lace in th e flu id tan k oara in th at t h e fl u i d m in us th e slu d ge a s durcped ou t b y ou r cu st o m e r , c o n t a in s l e e s b i s muth t l*m th e av e r age load, in the p l a n t * fu ch a y o ce d u r e seem s t o p u t on u n n ecessar y bu rden on th e fin ish e d m a t e r i a l , an d I m uld. 1 ii< t o d iso u sc w ith you th e p o ssib ilit y o f t ak in g st e p s t o remedy i t * bn step would probably cosisist in ageing the t e t r a e t h y lle a d sufficiently before it is blended into Et h y l fluid so that i t s b ism u th co n t e n t will be m o h lo w r r , probably around 0 ,0 1 , A second and independent step which would work in the same direction would be to segregate a l l sludges sonarated from tetraethyllead and Ytshyl iuid, u prouedur which I understand you are following at ;resent as far as filr-er-h* gs are concerned but which you have been unat-J e to follow in the c a se of r.totna still residues' a l t e r the 'r tcoh sr li !o t * I t * 1153 d i s t i l l * t ion o f such slu d ge s* I sea n ot su ffic ie n t ly fa n i l i a r w ith th e r -u':.- ,Vu o f cur plan ts to s&ico con cr ete sxxf^cistioois t o n silly a gr sall en closu re oox'.id bo vet asid e in ox o f the oiudjte p it s for th e aootaaula- t io n of such raaterissl (which run s bout bC0 bin -ruth ). Xf a l l such m at er ial can Vo socr ccat ed is. on ly 01 lo cat io n each in baton ;-:ou-*e and Deepwater, you i.'i.yht bo ab le t o r an a sp e c ia l batch from t i;*s to tiraa th rough th e olvrbxj d r ie r s sur.geetod by Houser* Another p o ssib ilit y w u ld probably bo t5e b u ild in g o f a sp e c ia l ssm ll size d si&olter which would bo capable o f ban dlin y wet slu d ge* .. Very t r u ly yourafe ; \ 0022310 LTD 39-45 RECOVERY OF 2LTRAfcTEirLIAD FROM TANK CAR SLUDGE PURPOSE To determine th e com position o f tan k oar slu dge and t o develop su it a b le methods o f recover in g t e t r a e t h y lle ad from i t . CONCLUSION 1 . Tank oar slu dge i s composed rough ly o f S<$ c o lid bismuth compounds, SQJ-o Eth yl Flu id , Q% le ad s a l t s , end 15/i kerosen e (u sed 'bo wash th e slu d ge from th e tan k o a r ). 2 . Eth yl Flu id and kerosen e can be recovered from t h is slu dge by steam d i st i l l a t i o n or by e xt r act io n vdth gaso lin e . *3. The recovered Eth yl Flu id con tain s 0,775? bism uth , based oa lo ad , which p r e c ip it a t e s ou t on st an d in g. 2bw sver, t h is sl'adge-form in g essspouad can be removed by air - age in g th e Flu id and f i l t e r i n g o ff th e pr e c ip it a t e which form s. . DETAILS According to a l e t t e r from l-!r. 7, H. Sch aefer o f August 31, XS39* slu dge i s forbad in t aak car s used fo r t r an sp or t in g Eth yl Flu id a t th e r a t e o f about 50.000 pem de per year freza th o Deepwater P le n t , m d t h is slu dge i s estim ated t o con tain ap p r o xim t ely 25$ t e t r a e t h y lle ad which i t i s d e sir ab le t o recover because o f i t s valu e and in order t o reduce p r esen t h&aards of dumping i t . Sis pr esen t in v e st igat io n m s isadertakeaa t o d et er mine th e probable cause o f th e ft esm tion o f t h is slu dge and t o d evise proper methods o f d isp osin g o f i t vM I b a t th e same time recover in g i t s valuable ccn atitu an ts. An alysis and d i s t i l l a t i o n . Five sam ples o f 2 l b . 6 o s. (1075 g . ) each were secu red fresa th e Manufacturing Department on August 11, 1939, A f i r s t sample o f t h i s slu d ge m s fi l t e r e d on a Buchner fu n n el, givin g a em ail amount o f f i l t r a t e and f a i r l y wet f i l t e r cab s. The f i l t r a t e m s an alysed fo r le a d , and th e cake m s t r e a t e d se p ar at e ly . I t ivas f i r s t ext r act ed vdth b esase t o remove t e t r a e t h y lle a d , th e hexene so lu t ion th en bein g washed vdth con cen trated assncaium h ydr cslde t o remove a sm all amount o f th e slig h t ly so lu b le t r ie t h y lle a d h a lid e . Th is was follow ed by e xt r act io n vdth benzene t o remove th e bulk o f th e t r ie t h y l lead valI d a . and th e so lid r esid u a was fr eed from so lv e n t . The t h r ee e xt r a c t s were an alysed fo r le ad , end th e so lid r esid u e m s an alysed fo r le ad , bismuth and h alogen . A se p ar at e sample o f th e f i l t e r cake was sub je c t e d t o steem d i st i l l a t i o n t o determine th e r ecover y o f t e t r a e t h y lle ad by t h is method. 'The r e su lt s o f t h ese t e s t s ar e shewn in Table I . KE" 0022311 Aaslysis of First Tank Car Slu.dgo Sample Total srsigfrfe of sample A, Filtrats 1, Bt-Fb (by Fb a n a ly sis) 2. Balance - hydrocarbons, etc Bo F i l t e r Csks En b r &et ioa 1 EtaPb - h essao s o l . fl I^OH i a s o l , 3 . Ets Fb3? - hercane s o l , , Mi^OH so l , 3 * Et^PbBr . b sn sess solu b le 4 , Dry esrbracted r e sid u e 3 084f( Pb 59,37>' Bi 3,52$ Halogen (as Br) 8 . Balan ce - h ydrocarbon s, e t c . Steem Bistillati on TotyxL Et^Pb v&*; 1 030 grama 260 So 920 .173 3.3 ci r** '9 >*A-tf*ril..^/0{ She high bisaasth content? of the residue after entr&otioa suggest that the tetraethyllead recovered from the tank car sludge sight contain a objectionable a x m n t of bismuth. She analysis of the snail samples available yielded negative results (because tbs analytical nsthod ana not suffioioatly sensitive) and therefore a sample of unfiltered tank car aiidgo m s subjected to steam distillation :o obtain & large sample of recovered tetraeth yllead. "'ABIE XI Steam Eistlllaticn of 520 g T i k Gar Sludge I>lstillatica Cloomtpforsaicttiioonnof<'*iF3"rdo'ac.foitriaoentao----n- 4 loro. . 3 hrs. Weight $ Pb % Br % Cl Sp, gr* at 20* 0 239 ge 2 7.4 24.6 5.0 1,395 29.3 g 47,5 2.0 1.330 "3 " K& 0022312 TABLE II (contd) Composition o f Fr act ion s 1st in action 4 M'S* 3 tiro 3. Coleu lated ocaposiidon Et^Pb C^lI^Er^ g 3h ^g i 3 Seroses Sp . gs>, ecn p u t sd frcrn estim ated ecsn positica !\.E^O 1.0 , yO 28,0 7.0 21.3 *l3S? 74o2 St `/a 2 04 ow 4 X.B2S 0 O ver all com position o f t o t a l d la t illa t Et^Fb Caii^ Br s CssSftCla Kerosen e ivt. J5^ L* so .a 46 c? 1 1 *1 4 0 ,? 7 t . JS Of d istillate 47.7 84 3 3 .9 81 u0 Tfe. $5 o f 17.6 0 ,8 2a 0 ,0 M iseries o f h alid es fe r lead n reosst 0,00 0.40 TOTAL 2.08,3 1 0 0 ,0 S7 ,,0 As shorn in Table I I , th e rat o f roeorozy taper ed o ff aXon ly, and i t took seven h ours t o e ffe c t approximate q u an t it at iv e rsoovn sy o f t b s v o la t il e le ad p r ese n t . ?h d i s t i l l a t e tvas an alyzed fo r Pb, Br , end C l, sad i t s correspon din g com poaiticn i a term s o f t e t r a e t h y lle a d , thylcs-io dibrcmld, eth ylen e di ch lor id e end kerosea i s a lso shcera i a th e t a b le . Sludge Fo z m t io a . The Flu id recovered by filt r a t io n ., e xt r act io n or st e sa SsH liH B.ce 'fo r m e d a w h it s p r e c ip it a t e im m ediately upon exposur t o a i r , and an alysis o f t h ese p r e c ip it a t e s shewed a la r ge percen tage o f h issaath * Th is slu dge form ation was in v e st iga t e d in th e follow in g manner, u sin g t3ie m at er ial recovered by 3teem d ist i l la t io n a Si p r e c ip it a t e pr esen t a t th e con clu sion o f th e steam d i s t i l l o t io n was fi l t e r e d o ff and a sample o f t h e f i l t r a t e was bubbled r d t h a i r fo r 24 h ours and th en allow ed to stan d exposed t o a i r fo r t h r ee days t o form more p r e c ip it a t e . The p r e c ip it a t e so fossaed was fi l t e r e d o f f , bubblin g isdLih a i r x a s con tin ued fo r m o t h er seven h ou r s, an d th e m at e r ial vias a lle ge d to st an d exposed t o a i r fo r seven days. An alyses o f t h e p r e c ip it a t e s, pr esen ted in Table I I I , shew t h at th e f i r s t ae r at io n tr eat* sisat p r e c ip it at e d a l l t h e sludge-form in g bismuth compounds. TABLE 111 P r ecip it a t e Soasad fey aer at ion o f d i st i l l i at e WtaSffiSo Jk,. X. Ferreed ciurla g d i st i l l a t i o n 0.71 4 6 *5 f50 iLr . 2* Z days ao r at i e n 3 days Storage 0.4S 34? 42,1 S. S 3 . X day fe r iisr ae r at io n * 7 days stor age 0S3 0 61.0 3.2 Total M ssu t h p r e c ip it at e d fren the c ist iila t e 0.2$# fenced cu d i s e l l a t e 0*,;7>a based or le ad * I t sh ould 1:0 act ed h ere -Suit bubblin g t e t r a e t h y lle ad alon e u?ltSx e it h e r a i r o r ouygea r e st slt s in on ly an eubre&ely slig h t aaoun t o f slu dge fbraaticaB, eirn ilar troatasn fc o f Eth yl Flu id r e su lt s in th e ready fojRsabico o f a slu d ge* r/hil th e presen ce o f bisjsn th c^noousds r e su lt s in cn e r t r r se ly r ap id fczm b io a o f a w h ite* voltsaiiicue p r e c ip it a t e An ign it io n t o st o f c. c a l l .353dpi o f th e *h dbs p r e c ip it a t e a ft e r bein g m sh ed Pith h exan es end d r ied iriciieated t h a t i t co n sist e d of e s organ ic t&ssrobh sx&do* r e scissio n o f h est jl t s "h e r sccvesy by solven t sebractica end by steam d ist i l l a t i o n i s i a rough agre-SEmt w ith th e r e su lt s r epor t ed in fr Sch afor*3 l e t t e r c f August 31* In which he st a t e d * "A batch o f about 2*000 lb s o f tuak car slu dge an alysin g sppresn afcGly 2o% t e t r a e t h y lle ad a s d i s t i l l e d l a th e e a p e r ia sa t a l b u ild in g* w it h th e roo very o f 600 Ifea. c f d i s t i l l a t e csialysiag about 80>S t e t r a e t h y lle a d ** E a t u r a lly , t h e acir n osit laa w ill r o sy from one t eak ear slu dge t o an oth er depending upon th e a^ - sa t c f solven t' txsod to wash th e slu dge fr sn th e tan k car * I t had bees an t icip at ed t h at th e sludge Eigh t oon oiat lar ge ly f Et3r bBr * i a which caso i t was eespeebed t h at steam Si st i l l a t l c n r ig h t y ie ld la r g e r sn or n t s o f Et^Fb th an -sore a c t u a lly p r e se n t on accoun t o f i t s forEsiti.cn by th e Trsll^kaoGa r e M st r ife u t io a r o h o t icai 2 St 5PbSr Et aPb -> B%?b2ra Etowsror* t h e per cen tage *cf -feriethyXs?<5 h r a:d d o i.j ver y m a i l * apprssdsafcoXy Z% in th e f i r s t tan k car oludgQ t &sp lo* and th e ccn sioten oy o f t oo slu dge ia suck t h a t oteem d ist i l la t io n d id n ot e ffe c t ICCpi r ecover y o f th e t e t r a e t h y lle ad p r esen t as su ch . Th is accou n ts fo r th e gr e a t e r *" y ie ld obtain ed by solven t e xt r act io n -vivan fey st e m d i st i l l a t i o n on th e fi l t e r e d slu dge fr e n th e f i r s t t eak car slu dge sam ple. 0022314 The h alogen p r esen t in th e o r igin a l slxidgo as t r ist h y lle & d h a lit e s cad le ad h alid e s i s c alc u la t e d as bromine because pr eviou s emp sr len oe h as shorn t h at th e ch lor id e ocat en t i s n e g lig ib le , the r e su lt s ar e ecmehat ap pr cxdm t s becau se o f t h e d iffic u l t y o f scou r in g r epr esen t a t iv e samples o f t h i s muddy slu dge ?i!tsa th e m e ly t ic a l d at a pr esen ted in Table I I , i t was p o ssib le t o r eeon st r u et th o c a a ^ o sit ia a o f tfee steam d i s t i l l a t e * Si calcu lat e d d en sit y o f a a d st a r e h avin g th e r econ st r u ct ed e02rp0sih l.cn was i s ver y good agrsesssset 'with th o observed d e n sit y o f th e st asia d i s t i l l a t e . I t w ill be observed t h a t th e sro v o la t il e o e n st it u m t a "ere ressyved by st e e a d i st i l l a t i o n durin g th e f i r s t fbta* h ou rs* w h ile t h e r ecover y o f th e t e t r a e t h y lle a d sad kerosen e t;ore pr obably n et o ak le t eve a ft e r seven h ours o f steam d i st i l l a t i o n . The d e c r i e s o f broads sad eh lcr in e pr esen t in t h e recovered fl u i d , 0*50 and 0*40, d iffe r from th ose o f t h e o r ig in s! fl u i d , 0*70 and 0*45, becauao th e etfcyien d lch lo r id e 3 th e m ost v o la t il e con st it u en t and p a r t ia l l y evaporated fr en th e t ask car b efor e too slu dge was removed, and tho t e t r a e t h y lle a d v.-as co t ocm plotely recovered because o f in caap le t e steam Sist illat io n cad decom position Ca th o b a sis o f th e above, ''he m t e r i a l recovered by ctecca d ist i l la t io n o f tan k ear slu dge appear s t o h e d o s e neigh in com position t o a sl ig h t ly d ilu t e d Eth yl flu id t o mis i t p e r m issib le t o Tjork i t o ff in sm ll percen tages in regu lar production Flu id . I t s sligh t ly h igh b isjnixbh con t en t , however, cak es i t ad v isab le t o ago th o m t e i l a l bofore blen din g u n t il th e p r e cip it at io n o f bismuth h as su bsided* The composition o f slu dge shows t h at i t s X'ccm t lcn i s duo t o th o presen ce o f himu&h l a th e o r igin al t e t r a e t h y lle ad * 1c-klng -the Ih au f&ebariag Department fs est im at e o f GO lb * elt 'dgs por xezik. c a r , o f vh ih 27% i s bismuth , t h er e must be 13 lb * o f Miusath p r ce ip lt at scl p ar tan k c a r , correspon din g t o about 0C3$ o f th e le ad * 'lx i-Mof lyrdbl^sz th en appear s t o be t o preven t th e presen ce ci* t h is b in sn h in th o Eth yl Flu id * I t s o r igin a ls irsxdcubfceeily th em ail c~cn r t o f blrm -th p r esen t c.e ca in p u r it y l a -She p ig lead * l a ad d it ion t o h ooping -tho speoii'loati-on s &a low- s b p o ssib le , syst em at ic st e p s sh ould m taken b remove th e bismuth sYoa th e produ ct* A ll th e slu dge oollcot od from f i l t e r s , vh eth er or n ot th ey ar e steam d i st i l l e d , sh ould co sm elted in a sep ar at e furitan e from th e lead recovery fu r n ace, an d th e sl a g ox* m etal recovered rh ot'ld *00 d ispor ed o f. The fo o t t h a t th e t e ak car slu dge con tain s a l o t o f fcicssath end ver y l i t t l o h alogen , and t h e fu r t h e r fa c t t h at th e ae r at io n p x*soip lt at es th e b im xt h p r e fe r e n t ia lly shows t h a t th e h alogen I s n ot rspon sib le f o r t h i s p r e c ip it a t io n , and t h er efor e i t sh ould be p o ssib le t o elim in at e th e t r ou b lo Try proper agein g o f th e t e t r a e t h y lle a d b efor e blen d in g. In a d d it ic a , th e h igh bismuth con t est o f th o slu d ge sa y g&ke I t n orth w h ile r ecover in g fo r th e valu e o f th e bismuth i t s e l f . P . *J. Eykatra 0 3 . Kurt 0, Calin gaort 10-10-39 AJK u r r fj K<? 0022315