Document 8Vb8wbmQdrbgxOVjzx5g3qdYa
S. X. DC PONT DE NEMOURS & CO. INCORPORATED
FIGMENTS DEPARTMENT
CC: C, E. Rossee - Wilm. J. E. Booge * " J* N, Tully - Newark A. Siegel - " J, H. Cooper - " C. J. Higgins 0. K. Cooper J, W. Mlnnich H. J, Rundell File 1.8 Wilmington File
Newport. Delaware April 14, 1954 MR. V. H. CHALQPSKI NEWPORT GREEN GX - "70 PROCESS'* Submitted herewith are sample operating forms foe* man ufacture of Green GX in the existing plant equipment as modified for "interim" production of this material. Also included are operating notes and data collected during the plant manufacture of Green GX in two campaigns of roughly 10,000 lbs, and 15*000 lbs. respectively. Selection of material for standardisation has been completed at Newark, and agreement reached with Sales that the change over from solvent milled to GX green can be made when the plant is ready. The Chemical Division completed its plant development work during the last campaign; therefore, it is requested that the Production Division assume responsibility for future plant manufacture of Green GX.
EFKJr:ad
Attach.
cA.
E. F. KLENKEV^R. CHEMICAL DIVISION
perm - 13
)ate Tine
GROPE QREEH "OX" CHLORINATION AND DRYINO Autoclave-201-A, 201-S Dryer 213-A, 213-B
Opr.
Instructions
Record
Quant:far St3t Ised
. .. . .
.
''
,
----------- -
1. Check autoclave-HT bottom valves closed
2, . ^St2art addit--ion of sulfur chloride-record --------- *
68.0-65 .0
~7
3. Finish addition or amrur chloride {
tens). In 201, 30UC or lower) 4. Fihish addition or dF crude
- . -M-R--IW#He
lot ^ ........IA>bV lot.. ........... Lbs. ..
~~Z ...
~1 1
-3W ----- &
tot
Lbs.
..........
5. Finish addition or copper chloride
6v Finish addition of Ohio Apex Alum. Chi.. """ "Y. Finish bolting head bn aiitbclave
m' w
8. Check operation of automatic valve. Set
a loo ps!
1
9. Meat charge to 50^0 with b^bl^SEbt' wat? r
10. At
shut orr hot water and allow ten
20 min. ''
to rise to &5-70uc reaction temp. When
reaction starts, put cold water on jacket
.ll'.'lfeeh venting OK at 100 p3i, reset con-
trolier to 200 psi, then to 2b5. After
pressure is under control at 265 pslj
"" start steam to autoclave jacket and heat
....... "ToT75C~ ~
1
" ""
--
12. start of 4 hrs'I bolding period at i7i>c -
min. and 2b5 psig min. Record max.ten. '
13. Endof holding period at l750;
Krs ; 4 hrs.
14. Pressure vented to 15. Charge cooled to
" psi TOU'psI m_;; 130C
16.
17. 18.
Vent
Dump Drop
pressure to
into rotary charge from
da30urytopecsrl-aisv_a_eltto(SroodtiuamrvChlod--1-_-----_----M-...n
30 DSi r:":
dryer
. _.
19. Allow 15 min. for charee to drop, then
add sulfur chloride flush to autoclave 20. Finish droDoine flush to rotary dryer
21. F.B. and back-up valve closed--autoclave
MP or heel
22. Start steam to rotary dryer jacket
(rouKhly 1/8 turn open) _
23. When vanor tern. reaches 70C --start
chlorine to dryer at minimum rate to hole ,
float suspended fabout 5Q-75#/hr.)
24. Heat dryer from 706C to 130cC in 1-1/2 hi 'S 25. When absorber temperature aeaks. onen
i. 1-1/2 hrs."
.lacket steam valve wide.
26. When vapor temperature drops to lipog (ti cm
____ -130C1 start chlorine to dryer at 100#7
_far. for 3-1/2 hrp.________ - ........ 27- Finish chlorine addition 28. Start C0o flush--leave steam on
(over j
hra . i***/ 4IU D * jI 11/2 hr.i
DUP050069706
N42039.01
>ate
Time CpT.
Instructions
wan Record star"
29. Start cooling water to dryer Jacket
30. Total hra. dried. 31. Start discharging crudetTom dryer
. lirs7 '
ItiaafceSBiJ
1 . 33. Record pigment weight--take 2 quart
' 1.....-
saimjie
... t
34. if druBaned use polythene lined drums &Lds {jiining must he m very good con* :
i | dltion
33. StenciJL lot no. and weights on drums--
.
Record drum weights
..........................1..............
Drum #1--Net weight '* u "..............
# w
!
fetal''Weight''
- JL--.
DUP050069707
GREEN GX FINISHING N-764
(Extraction-Distillation-Finlshing)
Batch Size - 1000# Crude Extr. - 219 tk.
Press - 35
Still - S25
Press - 4T
Mixer - 4|g
Cl No. ci No.
)ate Time Opr.
instructions
Quantity Record St" '"| Used
1. Check 219 tank--should he empty
1
2. Add water to 2I9tank
ii 30'`
iXEDKT
3. tMnpintd2I9 tank-G-~ "
... ... # t t t o --Smxr
4. Start 219 tank agitator ami stir for
1
2 "hours
--
"Erl' '2 hrs.--kraxr
5. pun the charge from 219 tank to 235 pres3(uae 3Iframes )-Run Aht press
1 1
filtrate to 237 tank. DoNot start
[
press washing b. Add water to 219 tank
1 it 30"
1 >xxxxxx
7. Cu e into 219 tank-G-
r ' ' "" '
o. Start 219 tank agitator & stir for
JTSurs
"ITW" 'tGOTST
.......
I
ErsT 2 hrs. mmr
9. Pumpcharge to 235 press--run all
press filtrate to 2Y tank "
lo. Flush 2i9 tank empty
li. Start 235 press washing, use' 40C wate1r
Run bleeding spigots to 23? tank
12. wasn ror ti nrs.; sample every 2 nrs.
HrsT 8 hrs. Bosssr
and record ohms--
/' Start
......
.. .
L. .
p ^Tipa.
: Record 2 4"lirs".'nT"
;!
ohms T b hrs.
, " "f 8 hrs.
13. Pump filtrate from 23? tank to 244
press--during 235 press washing cycle
TPT, 'Check 23? tank--pump allthe filtrate
to"244 press-flush clean
15. Add water to 237 tank
"20*----------
'*
'
16. Start S3? tank agitator
w"
"171 " Orop 235 press charge Into 237 tank
lo. Record final volume in 23? tank
*XOTX"~.J
19. Check 22$ Btill--must be empty. Ek>
no^ t>olt lid.
1--
20. Pump charge from 237 tank to 225 still
* 21. Flush 237 tank empty--watch volume in 225 still--45" mast. --hi? gauge
1
22. Record final volume in 225 still
Stibd c x
23. Close lid &'start still agitator 24. Add to 225 still--50j caustic-50"
xnm'VJ Rsr--" --l||l
251 Agitate for lO minutes--check pH 2o. Add 0d C6 - Ifeter-Before
After ...... .
n5H h iO nflET ot^oc
mxxx
-'WHET dOdQbaotx txxxtx
Added
xxxxxx 78 gal.
gal'
2?. Open lid with agitator on, then add:
Stearic acid Sodium Nitrite
itx&xLxixdx&xi'
m.......
30#
# #
Tri Cresyl Phosphate (celiuflex} TBQDSBr'Y-I7W~ --------
. ,,J.......
28. Check water spray
(over)
DUP050069708
QREEH OX FINISHING
Cl Mo. Cl No.
Pate Time .
Opr*
Instructions
Record
29 . Close lift, an* bolt turn ^ator onCOCB oond.
30* Open jacket steam Waive 2 turns (no
* sparger st^anii>. '
, ..- '...
31. When still bodv temp* reaches ?TC. .
--1 Ml1 U 1 ' El 11"1 iri'ny; i"M B'irryiy--
Pass valve*
32. Start water to still spray nozzle
(adjust to 5# below Inlet pressure.} 33. Regulate 3Ecket l>y-pasS vai.ve to Keep
' ' blit "&C1 not k o
above.151' still pressure.
....
34,' Add ' 1" at1 of"' cresyi phosphate
.. . fCeilurlex) to 23 stiTT'S hra.o anc[ ft hrs. after temp, reaches 90JC
Quantity . Std, used .
.--
,
.
--------: .
------
.
i
_,__ ;n 1______
................ .
,2 ft
hr. addition..... hr.addition......
ffXXXXXX sraxrxjB.
1 at. __' T'afT"
.'
a
35* Record distillation data every 30 min.
on attached sheet; 3b. When distillate samples show 2600 6tGB
.
in 500ec total sample, continue for 15
min* more, then resample. If the
resample Is the same the distillation Is
completed. Check by smelling vapor
from sample nozzle in vapor line*
37. Turn steam off--leave agitator oh 30. Check 241 press--should be empty a
clean--set u p 22 frames
MTftart ernsTas'lnsT to "151 presfTkeep ` I'.TM - pressure below SW/u, in.I. Run AM?
filtrate to 231 tank.
40. Finish pressing
>
41. Start press wai&ink--run all bleeding
. .
rrr-rvr-tn-
spigots to 231 .tank--sample filtrate
... -every_5..hrsj Record pH and ohms at-Stext
..............
...............
2 .hrs.
-- ft hrs.
0 hrs.
H hr.
10 hrs.
-. Hash.Jfc 2500 J2bmsOl\ 6 hrs. minimi M li.trate^r.<m_23i tank tSTapT'
3C2QUOQC 2500obme rrr-T'-'r-<rs<7T*
. ...ureas, during 2ftl &-aahln? cycled prefer-
ablyduriag 235 wash cycle) 43. Check ribbon miser--should be empty.
-n-Tr^r .
if not, flush it to 23I tank.
44. Dumb press to ribbon mixer.
4*,, Presacftke--Full i(yee. no ) Firm. '.......
............... 3lQnp%-raftard,.mtt,..,.Qf...fimBty.fr.epe.i_______
c~zirv..
DUP050069709
QRSEN GZ FINISHING
Cl No.
Cl NO.
Date
Time
-OP** .
Instructions
l&ariilty Record Std. Use
46. it necessary, add water to mixer, fflbc
Ihour'MnlmuH
gal. m ~]QESXE
.47. Recirculate last 1/4 hour of mixing
48. Start drumming from mixer--record pH ~W
40. Packed
drums. N-7b4
Lot
~ mxx "XDQS ism
50. Pack lot sample taken
51. uzap mixer flushes td"31' tak
GZ DISTILLATION DATA
DUP050069710
OPERATING* MOTES
The following la a condensation of the data In the summaries of the December 1953 and March 1954 campaigns and Includes information that will he covered in more detail In a future report covering plant development of the "70 process."
A - Chlorination
1 - Standard hatch size used to date--268# "as Is" CF blue, 268# AlCla, 3400# SxCl*, 30# CuCla. One hatch was made using 300# of CF crude and A1C1S, 30# CuCls and 3400# SxCix. No operating difficulties were encountered at either hatch size; a further increase In hatch size should he possible.
2 - Sulfur chloride, with % chlorine in the range 68.0-
69.0, produced satisfactory quality material.
In general the charges came up to pressure and
temperature more rapidly than standard type green
(Shs03 catalyst); however, there was no significant
difficulty controlling pressure.
I,, |
3 - Three chlorinatlons were made In which the standard ||
quantity (13-1/2#) of Sb^Oa catalyst was used in
f
the autoclave, and the 260# of A1C1S was added
L
to the rotary dryer before the autoclave charge m <
was dropped. This produced darkmasstone, blue
tint material by OX processing.
\
4 - Ohio Apex anhydrous A1C13 was adopted as standard after laboratory and some plant trials of other grades. Quality deficiencies and/or operating difficulties were attributed to the other types of catalyst tried.
B - Drying
1 - Early rotary dryer problems such as extended drying cycles, oaked charges, damage to dryer by excess ive bar movement, etc. were largely overcome by adding 300# salt (NaCl) to the dryer prior to dropping the charge from the autoclave. The use of lesser amounts (200 or 100 lbs.) did not give any signif icant improvement; 400# should be tried in the future to determine If additional improvement in dryer performance can be gained.
2 - A controlled rate of heat-up, plus early addition a of chlorine (see batch card), were found to reduce the over-all dryer cycle.
DUP050069711
C - Extraction
1 - Extraction at elevated temperature was found to be unnecessary, several batches of satisfactory quality material were produced by merely dumping the crude Into water and agitating without adding any steam. The heat resulting from hydrolysis of the Aids raised the temperature to approximately 50C.
2 - The only limit to the ratio of water to crude is ||
the punpabillty of the extracted slurry. The for- If
mula quantities worked satisfactorily.
il
D - Crude Filtration
,
1 - The ratio of 33# of crude (water extracted basis; /
or 74# on "as is basis) per cubic foot of 235 presb
volume worked well for the two long plant campaigns.
In general the cakes were good, and satisfactory
.
press filling and washing cycles were attained \ /
(see March 1954 summary). Should this step be
\j
a production bottleneck, washing eye lea of 4-6
hours should be tried.
2 - The only factors limiting the volume of reslurried presscake are pumpablllfcy and a volume limit in the still.
E - Distillation
1 - The original process called for the use of 0.65 lbs. 100# NaOH per 1.0 lb. CPC*,with a subsequent 1 hour stir period at 90C, followed by the addition of 1.0 lbs. orthodlchlorbenzene per 1.0 lb. of CPC* fcver 1-1/2 hour period). This was ultimately simplified to the use of 0.07 lbs, 100# NaGH/l.O lb. CPC*, with a subsequent 10 minute stir at roomtemperature, followed by the addition of 0.85 lbs. ODCB/l.O lb. CPC* over a 4-15 minute period. There was no noticeable change Th quality attributable to these changes.
The still slurry must be alkaline (pH 10.012.0) at the start of distillation or serious weak ness and dullness will occur.
2 - The sequence of addition of the ingredients indicated in the attached formula was established for optimum quality.
*Water extracted basis
DUP050069712
-3-
3 - An QDCB:CPC patio of less than 0.75:1 would adversely affect the rate of strength development; a ratio more than the formula quantity of 0.85:1 would lengthen the distillation oyole without significantly changing quality. A distributor should be used for best quality. The recovered ODCB is en tirely satisfactory for reuse "as is."
4 - The use of agents other than stearic aoid (Triton X-100, diglycol stearate, etc.) adversely affected rate of strength development. Lass than the stip ulated amount of stearic add (3# of the pigment weight, on a water extracted basis) caused quality degradation; more offered no advantage.
5 - The use of a water spray nozzle in the still, plus the addition of tri cresyl phosphate (roughly 0.1# of the pigment added initially and every 2 hours after the start of distillation) was found to sat isfactorily control foaming during the ODCB steam distillation. Dow Coming "antifoam A'1 was con siderably less effective than TCP. As additional insurance against pigment carry-over into the con denser, etc. with the risk of plugging the equipment, a demisting screen was installed in the vapor line leaving the still. This has functioned satisfactorily to date.
6 - Although volumes of approximately 60" (4*1500 gal.) have been distilled without difficulty,*^4-5" (4*1200 gal.) is a more desirable starting volume. ~~
7 - The still is best operated using the exit vapor pressure as a control. During the initial heat up, full steam can be used until a body tempera ture of 70C (max.) is reached. At this tempera ture the large steam valves should be shut off, and the small jacket valve used (no sparger) there after. using 15" of water as the maximum still pressure permissible, no foam-over should occur, and satisfactory still cycles should be attained.
8 - The distillation can be considered completed when the ODCB present in the distillate is 4# or less by volume (20ce/500cc or less). The still can be shut down when two consecutive samples (at least 15 minutes apart) indicate this end point has been reached,
P - Filtration and Packing
l - Filtration of the still slurry has been no problem. Estimating the required press volume per pound
DUP050069713
-/i' v.: (?> } ' -yfy^ ^i\-***(?.
3 /o/. fry. ? *^17# 2% ~
fr
/f* ///^ % 4- I / * tl
z 3O jSf&oO
7*1
2
(n^gf.
MtxiJ* */*??
DUP050069714
4-
of CPC (pack lot--dry basis) has been more difficult than for the crude. During the last campaign an I average of 885# per batch was pressed in 22 frames * in 241 press (+24#/ft.3), and the condition of the calces was fair. The average filtrate conductivity, toward the end of the cycle, was . as follows:
8 hours 10 "
12 n
14 '
1360 ohms 2200 " 2550 " 2770 "
Newark quality data Indicate 2000 to 2500 ohms is a satisfactory end point.
2' There were no problems associated with drumming this material.
0 - Quality and Yield
The following data were taken from the March 1954 plant campaign of approximately 15,000 lbs.
1 - Average quality (versus SW-3457-1, the temporary standard}
Masstone - Light
Strength - 98:100
Tint
- vvs blue, vs intense
5.3# Cu, 48.1# ci, 94.4# extracted solids,
2 - Over-all yield was 1.765# packed green/# blue crude
(100# basis).
^ /?^ ^4.
B - Special Haw Materials
1 - Anhydrous aluminum chloride--from Ohio Apex,
2 - Ortho diehlor benzene--from Crchem,
3 - Stearic acid--triple pressed--from Mark & Co., or Neofat--18-53--from Armour & Co.
4 - Tri Cresyl Phosphate--179A (Celluflex)--from Celanese Corp.
DU P050069715