Document NeVgnNDzggJK64bXXgM3nG1GQ
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vn i k
TEST AUTHOR.Z^Wfof^.cJ&lOOl.
'
Of f ic ia l PRODUCT n a me
t-Awlanthraciuinone (t-AAQ,^
/^ftcigs^ Pi&
PRODUCT CODE NO. 050-816-2000POUNDS PRODUCT PROPOSED
9,000
AREA
`'PonSOl" BUILDING NAME. ITPonSOlu Int.____________________________________________________
t it i p Amylanthraquinone - Modified Drowning & Neutralization________
PREPARED RY-.
Procedure : ^
~~yjy'^
D M. Crouse-
-' >
________________ ;_______________________________________'
RESPONSIBLE f o r t e s t an d t es t c q n c l u s io n :
D. S, James
PURPOSE OF TEST: To improve the AAQ yield by improving the recovery of AAQ/TCB solution through the wash steps.
The goal is to increase the TCB recovery from 67.8$ to 8l$ which could increase the yield to 8l^.
d u r a t io n o f t e s t : Eighteen (18) charges.
s t a n d ar d in v o l v e d : TMR-C-71-61, dated 6-16-72, TA-C-74-565, dated 8-7-74, TA-C-73-683, dated 8-7-74, TA-C-74-471, dated 8-7-74.
ANALYTICAL CONTROL: B No change Change described under Test Details
t e c h n ic a l b a s is f o r c h a n g e: See attached.
TEST DETAILS: (Include Safety ar.d Waste Disposal}
..
See attached.
r
SAFETY: The first neutralization should be monitored by supervision to make .sure no problems of overheating are encountered. None are expected (see Technical Basis).
WASTE DISPOSAL: No change in the nature of the waste, products is anticipated. A successful test will reduce the waste load sub
stantially.
DISTRIBUTION:
J,.L. Files S. C. Doberstein
D. 0. Miller (3) G. F.MacCormack
D, M. Crouse T. E. Lewis
C, H, Lake D. Putnam (3) -- D. S, James
A. F, Burk Group File (2)
SUPERINTENDENT, ANALYTICAL {When Required
DATE
SUPERINTENDENT, OYE QUALITY CONTROL IWrien flaq'dj DATE
AUTHORIZED EY: ' '
/
,,
SUPERINTENDENT. MANUFACTURING (Or Daloat)
. ^/
'S:'j
DATE
SUPERINTENDENT, TECHNICAL <tf Any)
MU-17E2-B-R6
Wr
/
OATE
i:
Page 2 - TA-C-74-1001
t-AAQ 11-5-74
TECHNICAL BASIS FOR' CHANGE;
Low yields in the AAQ process were traced to poor recoveries through, the wash steps (see Test Conclusion 73-683, dated 8-7-74). The cause of poor recoveries is probably.due to emulsions and slow settling rates leaving an 'interfacial layer
that is cut to the ditch containing AAQ in trichlorobenzene. Laboratory study of. settling rates suggested some improvements
in the work up procedure may reduce this possibility.
Settling Rates
The settling rates of a plant sample taken during the final wash were obtained as a function of the following variables:
temperature,
agitation time before allowing to settle and,
additives (NaCl, NagSOA, "Alkanol" surface active agent).
Hie final wash is a water wash after neutralization and has caused settling problems in the past. The experiments, done in triplicate, took 50cc of the AAQ/TCB solution and 50cc of the aqueous layer, agitated for a specified time and at a given
temperature (5 min,, 8oC. for the control) and then the settling time could be observed in a lOOcc graduated cylinder. Reproduci
bility was good.
The following results were obtained (OCHB-2839-100)
(a) Temperature - Increasing temperature increased the settling rate (Graph I). The process specifies
55-60 C. which appears to be a minimum. As the TCB layer settled out a large interface layer (emulsion)was observed. This was observed at all temperatures.
O) Agitation - Increasing the agitation time decreased the settling rate (Graph II) and also increased the volume of the interface layer.
Additives - Experiments with additives to break the emulsion and increase settling rates indicate up to 6$ salt* (NaCl or NagSOji) will substantially reduce settling times (by 70%) and eliminate the interface layer (Graph III). The surfactant "Alkanol" 1009 reduced settling time but did not eliminate the
interface.
Weight % salt in the aqueous phase,
'
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DUP050467719
DUP050467720
DUP050467721
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DUP050467722
Page 3 - TA-C-74-1001 t-AAQ, 11-5-74
Washing & Neutralization Procedure
The drowning, washing and neutralization procedure was modified using the following guidelines
(1) The salt content, Na2S04, will not drop below
the 3-5$ range.
.
.
(2) The temperature will be 75-80C. during the settling period.
(3) Agitation time is a minimum.
(4). Settling time is a maximum.
To do this the water washes after cutting the mother liquor were deleted., Neutralization at this stage will consume more caustic but make more emulsion breaking agent, sodium sulfate. It will also generate more heat. Laboratory experiments in a Dewar, flask gave a temperature rise of about 15C. when neutralizing 17$ sulfuric acid with 30$ caustic. This'should be easily controlled in the plant. Using the modified procedure (Table I) a slight improvement in yield was noted. The laboratory, however, has higher recoveries than the plant presumably because settling times are less and visual observation of the separation is possible. The amount of tar seems to depend on how much water is transferred to the distillation (more water means more
salts).
\
An estimated material balance through the washing steps in T-? and T-19 has been made in the Appendix A. The concentrations of sodium sulfate were defined. A comparison of the changes made in this test are shown in Table II. The recovery and yield is
the goal based on laboratory experience.
s
DUP050467723
.I
Page 4 - TA-C-74-1001 t-AAQ H_5_74
Technical Basis for Change (Coivt^cO TABLE I
i' AAQ using Modified Work Up Procedure
- Laboratory
...
. Current Work-up Test `Authorization
Procedures
Work-up Procedure
OCNB-2868
122
* 125
127
Reactants
ABBA, g . io solids
, * AI
4o6 4o6 406 12 12 12 9.8 9.8 9.8
Oleum, g *#
475 475 475 7.5 7.5 9.0
Product
Distillation
H20, g
TCB, g AAQ, g Tar, g
0 29 20 303 303 298
32 33 34 7 30 17
Total, g .fur, ppm
342
. .^95
369
-
nil
nil
TCB Recovery*, $
.85' 85 84
AAQ Yield**, % .
.76 78. 81
* Theory 357g '** Purity 88$ and theory 37g
/
DUP050467724
Page 5 - TA-C-74-1001
t-AAQ
11-5-74
1.
Technical Basis' for Change (Cont'd)
TABLE II
Comparison of Present & Proposed Work Up Procedure
Drowning 3 T-7
Present Process
Proposed Process
Drowning 3 T-7
Drowning, T-7
Wt. H2O, Its. ' Temp., C.
Agitation, hr. Settling, hr.
25,000 55 - SO
2
1
25,000 75-80
1
.2-3
Washing. T-19
Cut, T-19
Wt. HgO, lhs. Temp., C. Agitation, hr.
Settling, hr.
About 10,000 55 - 60
.4
1
None ' 75 - 80
None 1-2
Neutralization, T-19
Wt. H20, lhs. Temp., C. Agitation, hr. Settling, hr. Wt. WaOH, lbs.
10,000
55 - 60
2 100
Neutralization, T-19
12,000
75 - 80
* 2-3 3.000
Washing
Washing, T-19
Wt. H20 lbs. Temp., C. Agitation, hr.
, Settling, hr. Overall time, hr.
10,000 55 - 60
S' 2
8 3/4
7.000 75-80 ,
I-4
8 3/4 - 12 3/4
Estimated Recovery &. Yield
TCBRecovery, lbs./lot
AAQYield, lbs./lot , (100$) lbs./lot * Jf Total, lbs./lot
6, 321 67.8*
1,508
.1,211 60.0*
7,829
7,800 81**
1,800
9,60c"""
* TCB Theory 9,329 lbs., AAQ (100$) theory, 2015 lbs. see Appendix
TC-73-683. **TCB Theory 9,600 lbs., AAQ (100$) theory, 750 x O.85 x 3 = 1,913 lbs,
See Appendix A "Drowning" this test.
/
DUP050467725
Page 6 - TA-C-7^-1001
t-AAQ
II-5-74 .
TEST DETAILS:
Drowning ........... -
1* Charge 20.,000 - 25,000 lbs. of process water to T-7.
If the coil is not available 20,000 lbs. of water should be charged in Step (1) to assure `the temperature rises above 55C.
25,000 lb's, is preferred. Max. Temp, of process water- - 35PC.
2. With agitation on blow the charge from K-7 to T-7.
K-7 should not be above 95C.
3. Agitate the charge in T-7 for 0.5-1.25 hra at 55-90*0.
Preferred range is 75-8oC.
If temperature is below 55*0. steam should be passed through the coil to heat the charge or injected directly into the.mass.
,
Emulsions are likely to occur at temperatures below 55C.
Temperatures above 90eC. could lead to a fume
condition.
.
4. After'.1 hr. agitation, stop the agitation' and allow the charge to settle 2-3 hours before draining the water layer to the ditch from the top side outlet.
This leaves about 935 gal. in T-7 of which about 353 gal. is'AAG/TCB solution.
Sample the water layer for product by dropping a small amount of water layer sample into a large quantity of tap water and look for small droplets
of product at the bottom. If too much water layer sample is added the sample will be too dark tp
detect product.
5. After the water layer is ditched the TCB product layer is ready for transfer to the washing vessel.
DUP050467726
Page 7 - TA-C-74-1001 t-AAQ 11-5-74
I
4
6. Pump the charge from T-7 to T-19 7* Hold the charge in T-19 and repeat the drowning procedure
until three (3) charges have accumulated in T-19* Neutralization 8. When three charges are in T-19 heat to 75-80C., without
agitation and let settle for 1-2 hrs. 9. Transfer the water layer to the ditch from the bottom side
outlet of the upper set. This leaves about 1723 gal. in T-19 of which about 1059 gal. is AAQ/TCB solution. Check for the presence of product before ditching.
10. Add 12,000 lbs. of 55-60*0process water. Le
Temperature should^ 55-65C. after addition. 11. Turn on agitator and with temperature less than 65C.
neutralize the charge to a pH between 7.0 and^.O. Maximum temperature 90G. Approximately 3*000 lbs. 30$ HaOH needed.
12. Adjust temperature to 55-8oC. and agitat^e for additional 5-15 min., then allow the charge to settle at 55"8oC.
for 2-3 hours. Preferred temperature 75-8osC.
13. Transfer the water layer to the ditch as described in Step 9 above.
V
/
i
DUP050467727
Page 8 - TA-C-74-1001 t-AAQ, 11-5-74
Washing
l4. Add 5M-15M lbs. of 75-80C. water to T-19 and agitate for 5-15 min., then allow the charge to settle at55-8oC. for 2-4 hours. Preferred amount of water, JM Its. and settling time 3 hr. , and temperature 75-80*0.
15 Transfer the water layer to the ditch leaving the minimum amount of water with the charge.
The minimum water will probably be by cutting from the top-side outlet of the lower set leaving about 1084 gal. in T-19 of which less than 1050 gal. is AAQ/TCB solution. The sodium sulphate concentration should be 3-5^ in the aqueous phase.
16. If necessary to reduce the salt content add 5-15M lbs. of 75-80C. water, preferably 7M lbs., without agitation and allow to settle 1-3 hrs. followed by transferring the water layer to the ditch as in Step 15. DO HOT AGITATE. '
17. Charge is ready for transfer to S-9-
Page 9 - TA-C-7^-1001
t-AAQ 11-5-74
APPENDIX A '
Assumptions:
(1) T-7 & T-19 hold 33.4 gal./vertical in. of liquid (dia. 97").
(2) Side outlet height from base of tank.
Outlet No.
T-7
Inches
Gal.
T-19
Inches
Gal.*
15 19 23 28
w
-
501
635 768
935
15;9 24.2.
32.5 51.6 60.3 68,7
530 807 1084
1723 2012 2265
*Actually measured
(3) Density
Lbs./Gal.
Drowning, T-7
9.0% Oleum 17.4# Sulfuric Acid
Water a a q /t c b 30# NaOH
7.5# NagSOij.
15.5,
9.34 8.34
11.2 11.07
9.2 est
t
4,000 ABBA/TCB was 800 lbs. ABBA (20# solids) or 750 lbs. AAQ,
5140 9# Oleum x 102# H2S04 = 5243 lbs. H2SO4 (100#)
Volume organic:
4.000 - 50 lb. H20 = 3950 lbs./ll,2 = 353 gal.
Concentration aqueous
25.000 lbs. H20 + 5140 lbs. Oleum + 50 Lbs. 30,190 total lbs.
5243/30,190 x 100# = 17.4# sulfuric acid
DU P050467729
Page 10 - TA-C-74-1001
.t-AAQ ; '.i.v:
11-5-74
... '
'
Volume aqueous 30,190/9.34 - 323? gal.
Cut at 935 gal, (28" outlet) Therefore transfer to T-19 353. gal. AAQ/TCB 935-353 = 582 gal. 17.4^ H2SO4
. '.
.
Neutralization T-19
Combine 3 charges and cut at 1723 gal.
Have in T-19
3 x 353 1059 gal. AAQ/TCB
1723-1059 - 679 gal. 17.4$S H2S04
Caustic needed
**
679 gal. x 9.34 lb./gal. x 17.4^/98 lbs ./mole x 2 eq./mole
. - 22.52 eq. of acid
,
22.52 eq. x 40 lb./eq. * 30$
' = 3003 lbs. 30$ NaOH
Concentration of Na9S0A in Aqueous Phase
'
HpSOij. at start 679 x 9*34 6342 lbs.
H2O added
= 12000 lbs.
Caustic added
** 3003 lbs.
, 21345 lbs.
moles x 142 lbs ./mole = 1599 16s. Na2$Pi{. 1599/21345 = 7.5$ Na2S04
100
DU P050467730
Page 11 - TA-C-74-1001
t-AAQ. 11-5-74
Wash T-19
*
Cut at 1723 gal.
''
Assume 10$ AAQ/TCB lost
/ Have in T-19
1059 X 90$ = 953 gal. AAQ/TCB
1723-953 = 770 gal. 7.5$ Na2S04
Concentration NapSOk
770 Gal. x 9.2 HoO added
= 7084 lbs. 7.5$ Wa2S0i,
( 531 lbs 100$ Na2S02j 7000 lbs.
"14084.lbs.
531/14084 x 100$ = 3.8$'Wa2S04
Transfer to S-9
Cut at 1084 gal.
Assume 10$ AAQ/TCB lost
..
Have in S-9 953 x 90$ = 858 gal. AAQ/TCB (96l0 lbs.)
1084-858 226 gal. 3.8$ NS2S04
est. 226x9.2 x 3.8$ = 79 lbs. ITa2SQ4
Optional Dilution and Cut
Add 10,000 lbs. HgO = 1200 gal.
226 x 9.2/(10,000 + 226 x 9.2) x 79 = 14 lbs. NaaSO^
DUP050467731