Document LpyvrR9oRmavgMpJn2ew8K00Q
,r J, L Jt-sehor
. I, *u boat de '-'psaours h fo* Inc.
>r;'iv.\ic .`ji-ieistictils bivision iliningtcui* relaware
October Id, If3 9
i cfi.r Joe t
Yon may rvmovfoer that during ray last, vidits in Deepwater -we
discussed the proble.-a of tho disposal of
which accumulates
in tarJc c^rs, l m a' tachitt" hereto a Qdbyvr?~-eur"'report LTD y3945
coverin'" the invostirpitioxi of the oosaposition arid recovery of such &
sludge *
\>
^roa the point of
./V' V\
the hispurd involved it is clear that
otean distillation is -such. to shi^preferro$/io mere dumping of the sludge
itself, irrespective of the loHtion oif"the dune second point in
favor of the distillation is that\i\,f|/Sidg s. certain amount of recovered
fluid vf'.ioh is pretty pgjo^oxoept i\ir<a glightly oxvesoivs bismuth content
-.vhieh, lioiwver, can p~efys&3^y&\cut
by appropriate ageing on storage*
fven if ti-.is is i v-r^ivtx'vfti, tfsc^piendivi/ of a rraai 1 uncuat of such recover-
:-.-d fluid in regular /production wUhlc! not significant3.y raise the bismuth
content * i M
;-.eoordinn t.ckour calculations based on figures supplied by Mr* .nssornan, ^''S'rfcjLmte^th-gl^?s collected in tank: cers to correspond to 0*2ii} big&syth on the basils"#!1 the lead, which figure I understand it above tho a'/orage bismuth opatont of your pig load* inch a situation, of course, is bound ('to arise unr3$r your present practice, which 1 understand is to dump the steiou still rooiliyies of the distillation of sludge from Ethyl fluid or tetraethyllead rightyiafco one of your regular sludge pits* This can only lead to avjbuild-y#'.#? the bismuth content of your lead in process, the ul- ticsate refiMsf^-yrocess really taking place in the fluid tank oars in that the fluid ajinus the sludge as dumped out by our customer, contains less bis muth titan the average load in the plant, bush. a procedure seems to put on unnecessary burden on the finished material, and I would 1 i;< to discuss
with you the possibility of taking steps to remedy it*
One step -would probably cosisist in agoing the tetraethyllead sufficiently before it is blended into tthyl fluid so that its bismuth content "will be mch lowr, probably around 0,01, a second and independent
step which would work in the some direction v.-ould be to segregate all sludges sonar:-.tod from tetraethyllead and fishy1 iuid, u ^.rouedmro which I understand you arc following at present as far as filr-er-bs gs are concerned, but which you have been una-vje to follow in the case of r.taaa still residue' alter the
r i.l.bteoher "?i ' '3 3 ot* 1033
dlstilli tio.': of such slur :<??* I am not sufficiently fr-iiliar with the
er:f: i n of our plants to aatza oonoreto 3Ufx;cistians feasibly a small
enclosure could be yet aside in one of the slud;*e rite for the aootsaula**
lion of r/aoh raaterissl (which runs about 300 biu'suth)* If all such material
can to sarrypated ixi only one location each in 3ston
and roepwator,
you i.'i.yht bo all to ran a special batch x'rom ti;*j to time tJzrough the
olu'bjo drier * s\r,;:etod by beuger* Another possibility wuld probably
bo the Injilding of a special small sized eax>lter which would bo capable of
handling uet si'fdste.
c direr .Il.fch&efor . .*.&hee ,/
\
\ ;i
Kf 0022310
LTD 39-45
P. Dy&stra
5G3-KP-S3, 34,
9-2G-39
(
Approved by
RECOVERY OF ^TRW-j TEYLLEAD FROM TASK CAR SLUDGE
To detezraiss *2a eoiapositien of tank oar sludge and to develop suitable methods of recovering tetraethyllead from it.
CQmLVSlQU
1. Tank oar sludge is composed roughly of S<$ colid bismuth, compounds, 3 Op Ethyl Fluid* 5% lead salts, cud 15/i kerosene (used 'bo wash the sludge from the tank car).
2. Sthyl Fluid and kerosene eon be recovered freo this sludge by steam distillation or by extraction v&th gasoline.
-3. Tho recovered Ethyl Fluid contains 0.775? bismuth, based a load, which precipitates out on standing. IkKvsver, this sludge-romizig ecsspouad can b removed by air-ageing the Fluid and filtering off the pre cipitate which forms.
DETAILS
According to a letter fraa Mr. 7, H. Schaefer of August 31, 1839, sludge is forbad in tank cars used for transporting Ethyl Fluid at the rat of about SO.000 pounds per yeas* from the Deepwater Pleat, snd this sludge is estimated to contain approximately 25% tetraethyllead which it is desirable to recover because of its val3 snd in order to reduce present h&aards of dumping it. 2h9 present investigation ms undertaken to deter mine the probable ecus of the ftesmtion of this sludge and to devise proper methods of disposing cf it while at the aesae tins recovering its valuable constituents.
Analysis snd distillation. Five samples of 2 lb. 6 os. (1075 g.) each were secured from the Maaufoctia'ing Department on August 11, 1939.
A first sample of this sludge was filtered on a Buchner funnel, giving a small amount of filtrate and fairly wet filter cake. The fil trate ms analysed for lead, and the cake vma treated separately. It was first extracted tdth hosasss to remove tetraethyllead, the hexane solution then being washed with concentrated araseaiun hydroxide to remove a amount of the slightly soluble iriethyllead halide. Shis was followed by oxtruction with benzene to remora the b*alk of the triethyl lead iialids, and the solid residue was freed from solvent. The three streets were analysed for lead, end the solid residue ms analysed for lead, bismuth sad halogen. A separata sample of the filter cake ms sub jected to steam distillation to determines ths recovery of tetraethyllead by this method. Tho results of these tests are shown in Table I.
KE" 0022311
N22469.01
3MJ? 2 Analysis of First Tank Oar Slv.dgo Semple
Octal might of sample
1.080 grama
A* Filtrate
160
1. St^Fb (by Fb analysis) 3. Balance - hydrocarbons, etc.
38
SZo Filter Ces&q
920
Extraction
1. Et^Pb * hexane sol.,
inccl,
P EtgFbBr hexene sol.,, MH^GH sol.
o StaPbBy . bsassns soluble
Dry extracted residue
So 84fn Pb
63.27$ 31
3.52$ Halogen (aa Br)
Balsas - hydrocarbons, etc.
173
01
^ v" C
Stem ElstiUatian Et^Fb (by Pb analysis}
Et^Pb
/ V
T ri m*
3,1}
.4.
PA ,-pf
ti'j? p i ./O
19.35$ 17.13$
She high bismuth content of the residue after extraction suggested that the tetraethyllead recovered from the tank car sluc'ge sight contain
a objectionable amount of bismuth. She analysis of the snail samples available yielded negative results (because the analytical method ms not sufficiently sensitive) and therefore a sample of unfiltered tank car sltidg ms subjected to steam distillation to obtain a largo sample of recovered tetraethyllead.
TABLE XI
Steam X&stillail c m of 510 g Tank Car Sludge
A. Distillation
Composition of Fractions f-aaxfmwwfrr.^anat
ids fraction Sad fraction
4 hrs.
3 hrs.
Weight ft Pb % Br % Cl Sp. gr* at 20* C.
139 ge 2 7.4 34.6
8.0 1.393
29.3 g.
47.5
2.0
1.530
K'f 0022312
TAELE II (contd)
Composition of Fractions
1st fraction SridlmsS'S'
4 M'S*
3 ht o i,
3. Calculated composition
Et^Pb
Gs^Ss*a GpH^Ols
Seroses Sp. gs> eesputad from
estimated ecmpositlea
48,8 ist. 88.0
?B0
21.3
%
1.3S7
74.2 wfc.J5 2.4
28.4
l.SES
0. Overall composition of total cistdilate
lit. Vt JS of
Tst. $5 of Theories of halides
fa. distillate sludge
fer lead oreosst
C^?^3rs
^.vK&G'la Kerosene
83*2 46.7
11.2 40*?
47.7 34.3
5.9 31
17.6. 2.2 2e3
w8.0
0.00 0,40
TGT.it 188.S
S7,,0
As shorn ia Table 21, the rata of roocsezy tsperod off slowly. sad it took seven hours to offeot approximate qpsatttotlTe recovery of tbs volatile lead preseat* Th distillate was analyzed for Pb* Br, cad 01, sad its eorresgesding composition la terms of tetraethyllead* ethylene dtbrcmlde, ethylene diehlorids end kerosene is also shewn la the table.
Birdgo Formation. Th Fluid reeoverod by filtration, extraction or steam (CstSllation" formed a white precipitate immediately upc-u sposiir to air, and malysis of these precipitates shewed a large percentage of bismuth* 'This sludge formation was investigated in the follcaiug manner;, using the material recovered by atecm distillation 3
Si precipitate present at the conclusion of the steam distilla* tion was filtered off and a sample of the filtrate was .bubbled with air for 24 hours and then allowed to stand exposed to air for three days to form more precipitate. The precipitate so fossaed was filtered off, bubbling %'aUi sir tma continued for mother seven hours* and the material was alleged to stead exposed to air for seven days, tealyaes of the precipitates, presented in Table III, show that the first aeration treatmeat precipitated all the sludge-forming bismuth compounds.
-3-
0022313
TABLE III
Prselpitate foassd by aeration of distillate Tim uri-- . i n i in. <--iram my<wpug>iu^B-- srb.gms. $ Bi
% Fe
C* V~vb
Forced during distillation 0.71
46.5
83,0
?. days aeration, 3 days storage
0.43
84*7
48,1
*Hti
.fk
w
?> day further aeration, 7 days storage
0*23
0
61.0
3.2
Total bismuth precipitated frsia the distillate
0,1-^ honed ca distillate 0,': 7>a baaed oi loads
It should be acted here that bubbling tetraethyllead alone oddii either air or oxygen results in oaiy an enferetaely slight amount of sludge fczmfcU, similar troatasst of Ethyl Fluid results in the ready fessatica of a sludge, while the presence of bismth compounds results in cn ecrbrrsaly rapid fosmtioa of a whit, volmlnous precipitate* An ing&ticn tost of & call ccaiplQ of the a-Mts precipitate sfter feeing mshed with hessaxes said dried indic&ted that it assisted of m crgesi bismuth a:ddo*
Erscu33ico o f r e s u l t s
"3i rscevesy fey solvent acfer&etiea cad fey steaa distillation is in rough agre-SEmt with the results reported in 12?* Schaefor*3 letter of August 31, in whioh ho stated, "A batch of about 2S000 Its* of toak car sludge analysing sppresimfceXy 83$ tetraethyllead was distilled ia the e:uperi2i3atal lnd.ld3.ag, with the reosyezy of 600 lbs. cf distillate
csialyslag about 80$ tetraethyllead.* laterally, the osaositlea will vary from 030 teak car sludge to another depending vspoa the aaaanfe cf solo-sat used to wash the sluciga frsa the tack car*
It had been sabieigated that the aludg sigit consist largely of Et3FbDr, in which easo it was enpsoted that steam :Asb:U,lotion right yield larger snouats of Et-Fb than wore actually preseat on account of its ferities fey the well'-nsnsra reMstadfeutleei rotot-lcat
S BfcaFbBr EtaPb *> Et^HOra
Eo^s-cor, the percentage nf trie^yllea-d bre:ddo in aery mall, &ppro3dsatoly 8$ in the first tank car sludge sespl, sad ih ccnsioteszoy cf too sludge la ouch that esteem distillation did'not effeot XCG$ recovery of the tetraethyllead present as such. This accounts for the greater yield obtained by solvent retraction thaa by stem ciiutilisation on th filtered sludge from the first teak car slivJgo cozaplo.
*4**
0022314
The halogen present in Ifco original aliidgo as triethyllead halides cad lead halides is calculated as bromla tocsins previous ersperlenoe has shorn that the chlorl&e content is negligible, the results are ecmewhat apprenimts because of the difficulty of scouring represen tative samples of this muddy sludge. Frcta the analytical data presented in Table II, it was possible to recoaatruct the csspesitica of the sfeeaat distillate. The calculated density of a mixture hating the reconstructed compositeca was ia very good agrssssssct with the observed density of the stasia distillate. It will be observed that the mero volatile ecnstitiKata were removed by steea oistil2at5.cn during the first four hours, while the recovery of the tetraethyllead and kerosene were probably net oaklet eves after seven hours of steam distillation. The decries of tresis and ehlcrine present ia the recovered fluid, 0,20 and 0*40, differ fron those of the original fluid, 0*70 and 0*46, beoauao the ityleso dicklorida i3 the most volatile constituent and partially evaporated fren the task car before 'iftc sludge m reeved, and the tetraethyllead rats cot ompletely recovered because of incomplete steam distillation end decomposition*
On the basis of the above, ''fie material recovered by ctecca distillation of tank ear sludge appears to be close onsv&h in composition to a slightly diluted Ethyl fluid ts saalas it remissible to work it off in snail percentages in regular production Fluid, Its slightly high bis muth content, however, makes it advisable to ago 1ft material before blending until the precipitation of bismuth has subsided*
Tb.@ composition of sludge shows that its fccxns.d5.ca is ft;:? to the yreasaee of Msassfch ia the original tetraethyllead, liking 'she ihauf&etoriag Espartaffiat's estimate of GO lb. sludge <x>r teak snr, c >:$&& Z7% is bismuth, there must be 13 lb. of Muouth urceipitaSsd pas? tank car, corresponding to about 003$ of the lead* 'inn oMas* vroblsa Ifton appears to be to prevent the pross-neo ci* this bimsdft in th Ethyl Fluid* Its originals undoubtedly ths email c^cuct of birrarth proocah c.s ca inpurity ia the pig load* 2a addition to fceoijing ifto opeclfioati-ons as low s b possible, eysteasatio steps should to taken to ronove the hisnuth from tbs product. All the sludge ocllootod from filters, vhet&sr c-r not they are steam distilled, should bo smelted in a separate fusretao from the lead recovery furnace, and the slag ox- metal recovered should bo disposed of. '5xs fact that the teak car cl'idge coataims a lot of bicautsi end very little halogen, and the further fact that the aeration precipitates the l&emth preferentially shews that the halogen is not racpcaribl for IMs precipitation, and thsrefcre it should be possible to eliminate tbs trouble T?y proper ageing of the tetraethyllead before blending*
Ia addition, the high bismuth content of the sludge say snslc it worth while recovering for the value of the bismuth itself*
P. *J. Eyhatva C* 2. Surt 0. Calingaort 2.0-10-39
AoK
**#<
K 0022315