Supplementary information on production of ZR at Y-12


Material Information

Supplementary information on production of ZR at Y-12
Physical Description:
31 p. : ill. ; 27 cm.
Ramsey, J. W ( James W )
Whitson, W. K
Union Carbide Corporation -- Carbide and Carbon Chemicals Company
Oak Ridge Y-12 Plant
U.S. Atomic Energy Commission
United States Atomic Energy Commission, Technical Information Service
Available from the Office of Technical Services, Dept. of Commerce
Place of Publication:
Oak Ridge, Tenn
Washington, D.C
Publication Date:


Subjects / Keywords:
Zirconium   ( lcsh )
federal government publication   ( marcgt )
non-fiction   ( marcgt )


Information is given about production of zirconium at Y-12, supplementary to report Y-817.
Statement of Responsibility:
J.W. Ramsey, W.K. Whitson, Jr.
General Note:
At head of title: Carbide and Carbon Chemicals Company, a Division of Union Carbide and Carbon Corporation, Y-12 Plant.
General Note:
"November 15, 1951."
General Note:
General Note:

Record Information

Source Institution:
University of Florida
Rights Management:
All applicable rights reserved by the source institution and holding location.
Resource Identifier:
aleph - 005254811
oclc - 728098483
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Full Text




Subject Category: CHEM'STRY



J. W. Ramsey
W. K. Whitson, Jr.



November 15, 1951

Y-12 Plant
Carbide and Carbon Chemicals Company
Oak Ridge, Tennessee

Technical Information Service, Oak Ridge, Tennessee

Date Declassified: November 18, 1955.

This report has been reproduced directly from the best
available copy.

Issuance of this document does not constitute authority
for declassification of classified material of the same or
similar content and title by the same authors.

Printed in USA, Price 25 cents. Available from the
Office of Technical Services, Department of Commerce, Wash-
ington 25, D. C.

This report was prepared as a scientific account of Govern-
ment-sponsored work and is made available without review or
examination by the Government. Neither the United States, nor
the Commission, nor any person acting on behalf of the Commis-
sion makes any warranty or representation, express or implied,
with respect to the accuracy, completeness, or usefulness of the
information contained in this report, or that the use of any infor-
mation, apparatus, method, or process disclosed in this report may
not infringe privately owned rights. The Commission assumes no
liability with respect to the use of, or for damages resulting with
respect to the use of any information, apparatus, method, or proc-
ess disclosed in this report.





Mr. J. M. Herndon, Superintendent


Mr. G. A. Strasser, Superintendent


J. W. Ramsey
W. K. Whitson, Jr.


Information is given about production of zirconium at Y-12, supple-
mentary to report Y-817.

Oak Ridge, Tennessee

November 15, 1951


Supplementary Information on Production of Zr at Y-12

A meeting was held at Y-12 October 17-18, 1951 of representatives of firms

interested in obtaining information about zirconium production in order to

be able to submit bids for zirconium work requested by the AEC. A report

was compiled to present important facts about Y-12 zirconium operations,

Y-817, Production of Zirconium at Y-12. Tours of the zirconium plant at

Building 9211 were made by visitors and question-and-answer sessions were

held. In these sessions several questions were asked about points of

operation which it had not been possible to cover completely in prepared

literature or lectures. It was stated that these questions would be

answered in a supplementary report to be distributed later. This report

covers that information.

The following sections are included

A. Usage and Unit Cost of Chemicals

B. Purity Specifications

C. Typical Purity Values of Y-12 Feed and Product Materials

D. Operating Personnel Assignments

E. Power Requirements

F. Construction Costs

G. Pump List

H. Plant Operating Procedures

It should be noted that this information is issued supplementary to report

Y-817 and reference to that report should be made in studying the material

presented here.

A. Usage ano Unit Cost of Cnemicals

Tables .re prersented in Y-617, p.29 and 30, rnIich included coat figures 'or material coin into zirconium prouction. The fol0lowlag Ltale gives te unit
coat of matericil at tre market prices which existed at tre tif covered by ire [irEt compilation, and unit usage date calcul tea frrm t-.tal dollar iuaLe
and unit coat.

Period January, 1)51


Ammonrium Hydroxide
Hydrochloric Acid (CP)
Hydrochloric Acia (Tech.)
Hyarochloric Acid (Tank Car)
Sulfuric Acid
Ammonium Triocyanate
Zirconium Tetrachloride
Salicylic Acid
Natural Gas
Treated Water

Period July, 1950 thru April, 1951

Ammonium Hydroxide
Ammonium Hydroxide (CP)
Lime -
Hyarochloric Acid (CP)
Hydrochloric Acid (Tech.)
HydrocrhLoric Acid (Tank Car)
Muriatic Acid (Pound)
Salicylic Acid
Sulfuric Acid
Ammon um Ihiocyanate
Zirconium Tetrachloride
Caustic Flake

Natural Gas
Treated Water





Quant ty

li4.000 Gal.
17,600 Lb.
1.,2' Gal.
1,036 Gal.
5.536 Gal.
5,969 Gal.
61,600 Lb.
98,662 Lb.
2,556 Gal.
106,700 Lb.
3,581 M. Cu. Ft.
3,201 M. Lba.
5,465 M. Gal.
28 M KWH

116,500 Gal.
320 Lba.
225,600 Lbs.
13,499 Gal.
26,923 Gal.
737 Gal.
1,651 Lb.
842,750 Lb.
33,233 Gal.
547,200 Lb.
799,061 Lb.
17,765 Gal.
344 Lb.

27,271 M. Cu. Ft.
19,079 M. Lbs.
51,965 M. Gal.
248 u. KWH

Market Price
Por Unit

o0.1092/ga l.
0.8229, al.
0. 1083/'Ga 1.

0. 369''Lb.
0.2049/U. Cu. Ft.
0.4792/M. Lbs.
0.098/11. Gal.
4.785/M. rIC

0. 589/Lb.

0.21295/M. Cu. Ft.
0.56716/u. Lbs.
0.06312/K. Gal.
4.7L/ KWH

Units of UMterial
Per Pound of Zr

Cost of material
Per Lb. of Zr

0.L67 Gal. $0.051
0.565 Lb. 0.001O
0.0o57 Gal. 0.056
O.053 Gal. 0.010
0.11L Gal. 0.012
0.192 Gal. 0.021
1.98 Lb. 0.2)3
5.17 Lb. 1.129
0.08 Gal. 0.070
3.43 Lo. 1.251
0.108 M. Cu. Ft. 0.022
0.103 M. Lbs. 0.049
0.175 M. Gals. 0.017
0.0009 n. KWH 0.004
Pounds Ziroonium Produced as Oxide 31,134

0.47 Gal
0.001 Lb.
0.91 Lb.
0.054 Gal.
0.10B Gal.
0.030 Gal.
0.007 Lb.
3.-9 Lb.
0.13 Gal.
2.20 Lb.
3.215 Lb.
0.07 Gal.
0.0013 Lb.

0.11 M. Cu. Ft.
0.077 U. Lbs.
0.21 M. Gal.
0.001 M. KWH
Pounds Zirconium Produced as Oxide -




Cross Z1 r Zr 2 C
Product Section1 Strip Sponge ZrCl ZrO2 z

% Product (min) 0.19 99.8 99.7 98 97

Hf ppm (max) 0.51 100 100 100 100

N 0.11 50 50 .--- -

Al 0 120 120 30 30 4

Ti 0.11 80 80 100 100 5(

B 60 .1 .1 .1 .1
No chlorinated
C 0 500 500 carbon compounds --- -
less than 1% L
0 0 1000 1000 non-volati les -- n

Mg 0 20 500 -- --

P 0 5 5 200 200 31

S 0 5 5 50 1000 1(

Cl1 0.84 5 500 --- --- -

Ca 0 20 20 40 40 1

V 0.08 50 50 50 50

Or 0.05 100 100 100 100 1

Mn 0.21 50 50 10 10

Fe 0.04 700 700 150 150 101

Co 0.54 10 10 15 15

Ni 0.07 100 70 300 300 51

En 0.01 10 100 -----

Mo 0.02 200 --- -- --

Cd 24.4 .3 .3 .3 .3

W 0.09 50 ..

Cross Section max, barns .21
Hardness (10 mm ball, max 150
3000 Kg), min 80
1. Barns/atom Zr/% impurity; based on information in NYO-108 except Zr Cross
Section of 0.19 barns is used.
2. For direct melting into ductile, corrosion resistant ingots.






ass than








C. Typical Purity Values of Y-12


Typical Analysis of
ZrCl4 Feed From TAM

4 0.4

< 2
< 2


Average of Fifteen (15) Separate Batches, June, 1951

Average of Twenty (20) Composites, April to August, 1950

& Product Materials

Typical Analysis of Zr02
Product Materials From Y-12

< 0.2
< 2
< 100


D. Operating Personnel Assignments

The zirconium plant has been operated as outlined below. Insufficient

operating experience is available to clearly define the manpower requirements

for the permanent plant, which are expected to be less.

No. Shifts


Assistant Foremen



Feed Makeup &
Hf Processing

No. Men/f








Total Men





Total 28

E. Power Requirements

Except for gas heating, all power for the permanent zirconium plant is

electrical. Electrical costs for this project are obtained from allocations

of plant electrical costs made by the engineering department. These estimates

show power consumption by the permanent zirconium plant to be approximately

25,000 KWH per month. Based on five day per week operation, there are 520

operating hours per month. Thus the average power load is calculated to be

48 kilowatts. An estimated breakdown of power consumption is given as follows



Drives & Agitators

Venilators & Fans

APrcent of
Total Power KWH/Month

10 2,500

50 12,500

20 5,000

20 5,000

Total 25,000

Load Kilowatts





F. Construction Costs

The following table gives a breakdown of construction costs of the permanent

zirconium plant. Data are taken from accumulation of actual costs from labor

and material accounting in plant construction.

The permanent zirconium plant was constructed in the existing building 9211

and a number of tanks and pumps were available for re-activation, The amount

of this item is listed under "Existing Equiprent". Cost of the building is

not included. "New Equipment" includes that equipment purchased specifically

for construction of the permanent plant. "Labor" includes cost of labor

directly applicable to construction of the permanent plant.

Exist. Equip-& Total
System Equip. Mtls. Equip. Labor Tctal
Chem Supply and Storage $15,20 $-8.000 $21,20- 0 f ,000 $72,

Feed Makeup and Storage 24,900 25,000 49,900 25,000 '4,900

Extraction System 14,800 78,126 92,926 62,500 155,426

Ammonium Thiocyanate Recovery 4,200 12,000 16,200 4,000 20,200

Purification (Precip. & Filt.) 31,700 16,000 47,700 26,000 73,00O

Drying and Calcinincin 700 78,000 78,700 30,000 108,700

Hafnium Purification 6,600 8,000 14,600 6,000 20,600

Chlorination 24,100 27,833. 51,933 50,482 102,415

Waste Neutralization 2,100 5,000 7,100 2,019 9,119

Grand Totals $1?2,300 $257,959 $380,259 $213,001 $593,260

Cost of Labor Plus New Equipment $470,960

Total Value of Equipment and Installation $593,260

Go .- mp List

The following Pumps are in use in the permanent zirconium plant at 9211i

Thoryi t.4- .


(Feed Makeup Area)
6 Durichlor pump # X-2GSR-10O Duriron Co., Inc! 2 Process rraiser Pumps
Dayton, Ohio 2 Alternate Process Transfer Pumps
1 Mixer Pump
1_ 1 Surmp-to-Sewbr Pimp
2 Durichlor Pump # X-2MBR-60 Duriron Co.. Inc.; 1 Auramotia rrarnsfer Pump,
1 Filter Press Purip
4 Durichlor Pump # X-50R-62 Duriron Co Inc 1 Standby Sump Punp
2 Filter Press Pumps
1 General Utility Pump
1 Durichlor Pump # X-5MDE-7'-' Duriron Co., Inc.

5 Durco KA25 Pump # H-25MDR 52 Duriron Co., Inc! I Process Tr-risrer Pump
1 Alternate Process Transfer Pump
1 Mixer Pump
1 S4S. 516 Duplex # 5XDE Prop Pump {a Proportioneers Proportion NHLOH For Hf Preci=
Providence, R. I, pation Propor.ion Makeup
Phthtlate to Process
1 Durichlor Pump # X-2GSR-=10 Duriron Co., Inc ECI Supply Pump

(Extraction Area)
15 Centrifugal Pumps, Durichior X-2MBR-60 Duriron Co., Inc. 7 Beoster Pumps on Ex. Columns
7 Alternate Booster Pumps on Ex-
trac tion
I Acid Hexone Filter Press Pump
1 Duplex Proportioning Pump Milton Roy Corp. Proportions Cone- H2SO4 & H20
Ph ilaelphia, Pa tc Sulf'iric Stripping column
1 Duplex Porportioning Pump Milton Roy Corp. Proportioning Conrc. HC1 & H20
to BCl Stripping Column

Simplex Proportioning Pump

Simplex Proporticning Pump

Simplex Proportioning Pump

Milton Roy Corp,,

Milton Roy Corp.

Milton Roy Corp.

Proportions ZrOClp Feed to
Extraction Columns
Proportions Acidulate Hexone
to Bottom of No, 5 Extractor
Proportions Raw to
Bottom of' CUS Recovery Column


(Extraction Area)
1 Proportioning Pump Milton Roy Corp. Proportioninrg Makeup Hexone to
Philadelphia, Pa, Hexone System
1 Simplex Proportioning Pump Milton Roy Corp. Proportioning Acidulated Hex*.ne
from Filtered Acid Hexone Tank
to CNS Recovery Mixer Tank
1 Simplex Proportioning Pump Milton Roy Corp. Proportions Liquids from Over-
flow Tank into Top of No. 2
Stripping Column
1 Simplex Proportioning Pump Milton Roy Corp. Proportions NH4OH into CIS
Recovery Mixer Tank
1 Centrifugal Pump, Durichlor X-SOR-62 Duriron Co., Inc. Mixer Pump, CMS Neutralization
1 Simplex Proportioning Pump Milton Roy Corp. Experimental Work

(Purification Area)
1 # H-4 Wet Vacuum Pump (Nash Hytor) Nash Engineering Maintains Vacuum on Oliver Filter
1 Simplex Proportioning Pump (Hastelloy
liquid ends) Milton Roy Corp. Proportioning ZrOC12

1 Simplex Proportioning Pump (Haveg Liquid
Ends) Milton Roy Corp. Proportioning HC1

1 Simplex Proportioning Pump (SS. Liquid Milton Roy Corp. Proportioning Ammonium Phthalate
1 Simplex Proportioning Pump Milton Roy Corp. Proportioning Ammonium Hydroxide

1 Simplex Proportioning Pump Hill's McCanna Corp. Proportioning Ammonium Hydroxide
Chicago, Ill.
1 Duplex Proportioning Pump Milton Roy Corp. Proportioning De-ionized Water

1 Duplex Proportioning "Mini"-Pump Milton Roy Corp. Proportioning Ammonium Hydroxide




Simplex Proportioning Pump

Milton Roy Corp.

Proportioning De-ionized Water

Pump List Continued



(Extraction Area)
3 Durichlor (X-2MBR-60) C'ntrifugal Pump Duriron Co.. Inc. 1 Evaporator Head Tank Pump
2 Filter Press Pumps
1 Durichlor (X-2MBR-60) (35600 rpm) Duriron Co., Inc. Eimco Filtrate Trotnzfer
Centrifugal Pump

1 Durichlor X-50 R62 Duriron Co Inc, Precipitation Reactor Mixer
and Transfer Pump
1 Durco H-24 MBR656 (3600 rpm) Pump Duriron Co.; Inc. Oliver Filter Filtrate transfer
_____________L___________ i I______________ ______________________


H. Plant Operating Procedures

The following

sections are presented from the zirconium plant manuals

S-1 Feed Makeup

Z-2 Feed Makeup Control

Z-3 Filtering of Extraction Plant Feed

Z-4 Daily Inventory

Z-5 Extraction Plant Control

Z-6 Titration Methods

H-I Collection and Precipitation of Hafnium with Ammonia

H-2 Filtering of Hafnium Hydroxide

H-3 Rewashing of Hafnium Hydroxide Cake to Remove Sulfate

H-4 Dissolving of Rewashed Hafnium Cake in HC1

H-5 Precipitation of Hafnium from HC1 Solution

H-6 Rewashing of Hafnium Salicylate

Operating procedures for the purification facilities, calciner and dryer

are still being developed and are not presented here. Certain changes will

be necessary in the feed make-up procedure as a result of thiocynate recovery

and recycle.

Z-1 Feed Makeup

Feed solution for the extraction plant is made up at the tank farm by dis-

solving crude zirconium tetrachloride (ZrClL) in water. Ammonium thiocyanate

(NH CNS) and ammonium hydroxide (NH OH) are added to the zirconium solution to

prepare it for extraction. Tank 9 or Tank 12 are used for this operation.

After the solution is prepared, it is pumped through a filter press to remove

any undissolved solids and then stored in a tank (No. 3) ready for plant use.

Because plant operations may make it desirable to vary the size of feed batches,

formulas are provided here for 500 gallons and 800 gallons.

Final Gallon in Batch 500 800

Gallons Water at Start 350 550

Lbs. ZrC4L 1380 2200

Lbs. NH40H 385 615

Lbs. NH CNS 850 1350

This should give a concentration of approximately 1.05 lbs. Zr/gallon solution

and approximately 2.5 molar CNS and 1 molar HC1 in the solution,

1) Check with shift foreman to determine size of feed solution batches required.

a) It is desirable to not make final adjustment and filter feed solution

more than 16 hours ahead of actual plant needs.

b) Shift foreman will decide whether the 500 gallon or 800 gallon batch

is needed.

2) Measure water into empty tank

a) Either Tank 9 or Tank 12

b) Record batch number, time started, etc. on Daily Work Sheet

Z-1 Feed Makeup (Continued)

3) Adjust depth of ZrCl4 discharge hose into tank until it is about 2 inches

under surface of water, tighten down wing nuts on packing gland to hold


4) Clamp down hinged section of tank port.

5) Turn steam and water on ejector.

a) On platform just outside building

6) Start circulation pump to agitate solution in tank. Pump out of the top of

the tank into the bottom through the heat exchanger. Be sure that the

cooling water is on the heat exchanger.

7) Prepare drum of ZrC14 for unloading.

a) Set drum on scales and check gross weight

b) Turn on exhaust fan

c) Remove lid from drum

d) Gas mask and elbow-length rubber gloves are required safety equipment

for this job

8) Swing ZrCl4 unloading hose into drum and let the vacuum draw the ZrClL powder

into the tank.

9) When drum is empty, check tare weight and subtract from gross weight to get

net weight of ZrCl4 in drum. Repeat 6 and 7 until 3/4 of the needed ZrCl4

for the complete batch is in the tank.

10) Using the ammonium hydroxide measuring tank, add the full amount of ammonium

to the batch.

a) Record ammonium hydroxide added on Daily Wark Sheet

11) Add remainde. of ZrCl4 up to full weight required for batch.

a) Record ZrCl added on Daily Work Sheet

Z-1 Feed Makeup (Continued)

12) Using the same method as when adding ZrCl draw the required amount of

ammonium thiocyanate into the tank.

a) Record total weight ammonium thiocyanate added on Daily Work Sheet

13) When all chemicals are in the tank, check total gallons and if necessary,

add water up to final gallons of formula.

1h) When batch is completed, continue to agitate for 30 minutes. Then:

M Cut down steam on ejector, leave enough to provide slight vacuum.

b) Open tank port

15) Take 100 ml sample of batch

Z-2 Control of Extraction Plant Feed

It is extremely important that each batch of extraction plant feed meet these


Specific Gravity 1.28 to 1.30

Lbs. Zr Per Gal. 1.00 to 1.10

Molarity of HC1 .80 to 1.2

Molarity of CMS 2.45 to 2.55 or as specified

1) After a feed batch is completed and sampled, the operator will take the

sample to a titration table and:

a) Check specific gravity and record on Work Sheet

b) Titrate for molarity of HC1 and record. See "Method for Titrq+i.g in

Feed Solution".

c) Titrate for molarity of GCS and record. See "Method for Titrating

Solutions for CMS".

Z-2 Control of Extraction Plant Feed (Continued)

2) Now re-sample the batch and another operator will run a check titration on

the solution for HC1 and CNS.

a) If the solution was well mixed and both sets of titrations are accurate,

the answers should check with 0.05

b) If the answers do not check, take a third sample of the batch and again

titrate. This should establish which of the first answers is correct

3) If the final control measurements do not fall within the limit set up, the

batch must be further adjusted. In this case, contact the shift foreman

for directions;

4) For best plant operation, it is desirable that each feed batch be completed

and sampled far enough in advance of plant needs that the analytical answer

in lbs/gal. is reported.

5) It is the responsibility of each operator to see that all information con-

cerning any part of an operation is properly and promptly recorded on Daily

Work Sheet. At the end of the shift, the operator will check his work sheet

to see that all items are complete for his shift, including time, signature,

etc. All samples sent to the analytical laboratory must be recorded in the

sample log book as well as on their respective work sheet.

Z-3 Filtering of Extraction Plant Feed

1) No. 1 filter press (NE corner) is used for filtering feed solution.

2) When a batch is ready set valves at tank and at press to circulate

through filter back to makeup tanks.

Z-3 Filtering of Extraction Plant Feed (Continued)

3) Start cumnp (wth t:,'-pass open so as not to put too much pressure on press)

and let solution from press return to feed makeup tank for a few minutes

until it becomes clear. Then change valves to put the solution in Tank

No. 3 (filtered feed salvage).

4) Continue to filter entire batch or part batchn, depending upon plant needs.

a) Be sure and record time started filtering and by whom and time finished

,filtering and by whom

Z-L Daily Inventory

1) At 700 Al1 each morning the operator coming on shift will take an inventory

of solutions in all tanks in the tank pit and the extraction plant head

tank on the third floor.

2) This inventory will be recorded in space provided on the Daily Work Sheet

for feed and product collected.

a) On the sheet for the day ending, record the inventory under Ending

Inventory. Record the same information on the new sheet under Be-

ginning Inventory.

Z-5 Extraction Plant Control

1. Concentration and rates of extraction solutions are checked every two to

four hours at important control points in the extraction system. Values

are obtained by sampling solutions and analyzing6 for components. Simple

analyses are run on samples by plant operators and more complex analyses

are run on samples submitted to the production analytical laboratory.

2. Control points and measurements are listed as follows:

(A) Zirconium Product Stream
(1) Zr Concentration Lbs/gal.
(2) Hafnium Concentration PPM
C) NS Concentration Molarity
(B) Hafnium Product Stream
(1) Concentration Hf Lbs/gal.
(2) Zr Concentration PPM*
() CNS Concentration Molarity
(C) Aqueous Solution from Stripper No. 1
(1) CNS Concentration Molarity
(2) Soecific Gravity

(D) Aqueous Solution from Stripper No. 2
(1) CNS Concentration Molarity
(2) Specific Gravity

(E) Aqueous Thiocvanate Solution from CNS Reccvery Neutralizer
(1) PH
(2) Thiocyanate Concentration Molarity
(3) Flow Rate GPH
(F) HC1 Feed to Stripper
(1) HC1 Concentration Molarity
(2) Flow Rate GPH

(G) H2SO Feed to Scrubber
(1) Concentration H2SO4 Molarity
(2) Flow Rate GPH

Sample to Analytical Laboratory.

Extraction Plant Control Continued

(H) ZrOCl2 Feed Solution
(1) CNS Concentration Molarity
(2) Flow Rate GPH

(I) Hexone from Thiocyanate Recovery Column
(1) CNS Concentration Molarity

(J) Hexone from No. 1 Extraction Column
(1) CUS Concentration Molarity
(2) Specific Gravity

(K)SHexone from H2SOL Scrubber Column
(1) CNS Concentration Molarity

(L) Hexone from CNS Recovery Neutralizer
(1) CNS Concentration Molarity

(M) Hexone to Extraction Columns
(1) Flow Rate GPH

(N) Hexone to CNS Recovery Neutralizer
(1) Flow Rate GPH

(0) Hexone to CNS Recovery Columnj
(1) Flow Rate GPH

(P) Pcw Hexone to Plant Makeup
(1) Flow Rate GPH

5. Operating limits of control variables and

indicated by the following values.

of Sampling

A-1 Zr Product Lbs/gal. 2 Hrs.
A-2 Hf PPM
7 "I

OjS molarity

Hf Product Lbs6&al.,
CNS Molarity

No. 1 Stripper CNS

1f Hrs,

2 Hrs.

frequency of sampling are as

Av. Value

0.40 M

.25 M

Variation Limits

0.7-0.8 -
50-250 500
.55-45 -

.035-.0o5 -
1000-O.0,00 -
.20-.30 -

.55 .25-.45 -
1.055 1.045-1.065 -

Extraction Plant Control Continued

Frequency Normal
of Sampling Av. Value Variation Limits

D-1 No. 2 Stripper CNS
Molarity 2 Ers. 2.8 2.2-3.2 -
D-2 Sp.G. 1.300 1.27-1.33 1.25-1.35

BE- CNS Solution paH Hrs. 7.0 6-9 4-10.5
B-2 CNS Molarity a 2.5 2.2-2.8 -
E-3 GPH 25 20-30 -

F-1 HC1 Molarity 2 Hrs. 3.5 3.4-3.6
F-2 GPH 22 19-25

G-l H2SO Normality 8 Hrs. 5.0 4.5-5.5
G-2 GFH 30 28-32

H-i Feed CNS Molarity 2 Hrs. 2.8 2.7-2.9 2.6-3.0

I-i Hexone CNS Mol. 2 Hrs. 2.4 2.0-2.8

J-1 Intermediate Hexone
CNS Mol. 2 Hrs. 2.8 2.4-5.2
J-2 Sp.G. .916 .905-927

K-I Scrubber Hexone CNS
Mol. 2 Hrs. 2.3 2.0-2.6
L-i CNS Recovery Hexone
Mol. 2 Hrs. 0.1 0.0-0.2 0.2

M-i Entering Hexone GPH 4 Hra. 100 95-105

N-1 Hexone to Neutralizer
GI[ 4 Hrs. 40 35-45

0-1 Neutralized Hexone GPB 4 Hrs. 40 35-45

P-i Hexone Makeup GEP 4 0-10

Extraction Plant Control Continued

4. Sampling: Samples are of two types:

a. Spot samples: Take sample from sampling valve in line. First drain

valve and discard. Then take sample in clean sample bottle.

b. Tank samples: Use vacuum samplers provided. Return first portion

sampled to tank. Then take sample in clean sample bottle.

5. Chemical Analysis: Procedures are given for testing acidity and CNS

concentration in various solutions in Section Z-6 which follows.

6. Flow Measurement Method: Flow measurements are made by either of two

methods depending on the line and tank arrangement.

a. Measure time to fill one pint measure.

Rate (GPE) = o50/sec.

b. Measure gallonage tank change in two hours.

Rate (GPH) = Gallons/2

7. Corrective Measures for Plant Control: In general, follow limiting

values listed in Section 3. Specific measures for plant control are

outlined below.

a. A-2 Hf PPM. When Hf exceeds 500 ppm, notify foreman immediately.

If value is very high and plant has been known to be out of balance

for appreciable time, flow should be diverted to tank reserved for

high Hf product until balance is restored to columns.

b. D-4 No. 2 Stripper Sp.G, If Sp.G. varies outside limits 1.25-1.35

and values are consistently high or low with CNS molarity, HC1 rate

is indicated to be off. Condition should be corrected by making

small changes in HC1 pump rate at thymatrol control positioner,

Extraction Plant Control Continued

c. Any high or low values of variables listed in Section 3 should be

noted and immediate measurements should be made of related values

in order to obtain a correct diagnosis of troubles. Any of these

values out of control for an appreciable length of time will be

reflected in subsequent values of product purity. By attention to

plant control measurements, operating personnel should find and

correct any bad conditions before product is affected.

Z-6 Titration Methods

1) Method of Titration of Acid in Zirconium Feed Solution

The calculations in this titration are set up for the determination of acid in

zirconium-hafnium mixture analyzing 2'% Hf.

Pipette 2.0 ml of sample into 75-100 ml of distilled water. Add 10 drops of

brom-cresol purple indicator. Titrate with 0.5 N NaOH until a definite purple

end point is reached. (pH 6.5). The acid concentration is calculated as follows:

acid normality (ml of NaOH)(N of NaOH) 2.35 (#/gal of Zr)
(ml of sample)

In the past the feed solutions averaged 1.05#/gal. Zr.

2) Method of Titration of Acid Concentration of Hydrochloric Acid and Sulfuric

Acid Feed Solutions

Pipette 2.0 ml of sample into 50 ml of distilled water. Add 4-5 drops of

phenolphthalein indicator. Titrate with 0.5N NaOH until a pink endpoint is


If the hydrochloric acid feed solution contains ammonium thiocyna~te, methyl

orange indicator should be used in place of phenolphthalein. In this case the

endpoint is a change from orange to yellow.

The acid normality of the solution is calculated as follows:

N = (ml of NaOH)(N of NaOH)
(ml of sample)

3) Method of Titration of Acid in Hafnium Feed Solution

The calculations in this titration are set up for a zirconium-hafnium mixture

analyzing hO% Hf.

Pipette 2.0 ml of sample into 75-100 ml of distilled water. Add 10 drops of

brom-cresol purple indicator. Titrate with 0.5N NaOH until a definite purple

Z-6 Titration Methods (Continued)

3) Method of Titration of Acid in Hafnium Feed Solution (Continued)

end point. (pH of 6.5). The acid concentration is calculated as follows:

Acid Normality = (ml of NaOH) (N of NaOH) 1.68 (#/gal of Zr-Hf Soln.)
(ml of sample)

At the present time the feed soln. analyses about 0.63#/gal.

4) Method of Titration of Solutions for Thiocyanate

Pipette 2.0 ml of sample into a 25 ml volumetric flask. Dilute the sample so

that the bottom of meniscus coincides with the mark on the stem. Dilute the

sample with distilled water if it is an aqueous solution or denatured alcohol

in the case of hexone solutions. Shake the flask well. Pipette 1.0 ml of

this solution into 50 ml of diluted hydrochloric acid (1 part 12NHC1 to 4 parts

distilled water). Add 4-5 drops of ferroin indicator. Titrate with 0.IN ce(HSO)0

until the light blue end point is reached. The thiocynate molarity is calculated

as follows:

M of NS = [ml of Ce(HS0) 'a x factor.

For a 0.1000N Ce(HS04)h solution the factor is 0.2083.

H-1 Collection and Precipitation of Hafnium with Ammonia

In the Extraction Plant, hafnium is extracted from the feed solution into the

hexone, and in the scrubber it goes from the hexone into the sulfuric acid

stream. The sulfuric acid is taken to the Tank Pit and collected in either

Tank No. 11 or No. 14.

1) Collect the sulfuric acid (containing the hafnium)in one tank for a 24-

hour period.

a) Change over to an empty tank at 7:00 AM each morning

H-i Collection and Precipitation of Hafnium with Ammonia (Continued)

2) With the metering pump (P-2), continuously feed a stream of ammonium hy-

droxide into the same tank that is collecting the sulfuric acid (No. 11 or


*a) This should be adjusted to maintain a pH of 7.0 to 8.0 in the collection


b) Maintain air agitation on the tank to get proper mixture of the solutions.

c) ammonia added to the sulfuric acid will give a slurry of hafnium hy-

droxide and water.

H-2 Filtering of Hafnium Hydroxide

1) At 7:00 AM each morning change the sulfuric acid from the plant and the

ammonium hydroxide from metering pump (P-2) into the empty tank.

a) Mark up Daily Work Sheet showing the change-over

2) Agitate the tank full thoroughly with a circulation pump for 15 minutes.

3) Take a sample of the mixture in the tank and check for pH.

a) If pH is correct and slurry is settling out of solution, the batch is

ready to filter

b) If pH is low and solids do not settle more ammonia is needed. This must

be corrected before starting to filter batch

4) Start filtering the mixture through the steel filter press (center, east


a) This is No. 2 press

5) When press is full, shut off pump, and using air for about 5 minutes, blow

excess filtrate from press

H-2 Filtering of Hafnium Hydroxide (Continued)

6) Wash cake in press for about 10 minutes with water. Repeat with air for

5 minutes.

a) Water on line on press

7) Wash for additional 10 minutes, use air again and for about 10 minutes after

water stops coming out of press.

8) Break down press and drop cake into stainless steel dolly. Transfer cake

to clean drum and label.

9) Repack press and repeat procedure until the tank is empty.

a) The hafnium hydroxide cake will probably be high in sulfate (SO4) which

will have to be removed by further washing.

H-3 Rewashing of Hafnium Hydroxide Cak- to Remove Sulfates

1) Put 200 gal. water into reactor

a) Tank No. 15 or No. 16

2) Add 300 to 350 lbs. hafnium hydroxide cake

a) Have agitator going when adding cake

3) When cake is all in the reactor, agitate for 30 minutes, or until all cake

is thoroughly mixed.

4) Filter through rubber press in SE corner. Repeat filtering and washing

procedure as in II.

a) This is No. 3 press

5) Put cake into clean wooden drum. For each drum full, sample and request

ibs. Hf/lb. and % SO0. Weigh and label "Washed Hf Cake.

A. R # Net Wt. ."


H-3 Rewashing of Hafnium Hydroxide Cake to Remove Sulfates (Continued)

a) List each drum No., A. R. #, net wt., etc., in log for rehashed

Hf cake.

H-4 Dissolving of Rewashed Hafnium Cake in Hydrochloric Acid

1) When 1500 to 2000 Ibs. of rewashed hafnium cake is collected and the analysis

is aqpilable, prepare to dissolve it in hydrochloric acid.

2) Make a list of all drums ready for dissolving. Total weight of hafnium metal

in each of the drums.

a) This information will be in the washed hafnium log book

3) For each 5 pounds of hafnium metal in the batch, add 1 gallon HCQ in a


a) Either Tank No. 15 or No. 16

4) With the agitator going and using a wood and rubber loading funnel, add the

cake to the reactor.

5) Heat to 70-80o C and continue to agitate until solution becomes clear.

6) When solution is ready, filter through No. 3 press and collect the solution

in Tank No. 13.

a) Tank No. 13 to be used for storage of dissolved hafnium only

H-5 Precipitation of Hafnium from HC1 Solution

1) Sample solution in T-13 and get lbs. Hf/gal.

2) When analysis is available, pump enough of this solution into either T-15

or T-16 to have 50 lbs. hafnium metal.

H-5 Precipitation of Hafnium from HC1 Solution (Continued)

a) Divide 50 by the number of pounds hafnium per gallon to determine the

number of gallons needed

3) Add enough water to bring the total gallons in the reactor to 250.

4) Turn on agitator drive.

5) Add 90 lbs. salicylic acid.
6) Turn on steam and bring temperature to 800 C.

7) Hold this temperature for 30 minutes aging period.
8) Filter through No. 3 press.

a) Take continuous drip sample of filtrate from press

b) Make a composite sample of all filtrate from precipitation batch

c) One precipitation batch will make several press batches of cake

9) While the batch is filtering, make up wash solution in the other reactor

(T-15 or T-16, whichever is not used for above)

a) Use: 200 gallons water

1 gallon HCI
2 lbs. salicylic acid

10) When press is full of cake, use the same pump and wash the cake with 100

gallons wash solution.
11) Dry cake thoroughly. Approximately 15 minutes after water stops coming from


12) Break down press and drop cake into clean dolly.

a) Transfer into clean drums and hold until ready to rewash

H-6 Rewashing of Hafnium Saljcylate

1) Put 200 gal. water into a reactor and prepare as wash solution and start


a) Add: 1 gal HC1
2 pounds salicylic acid

2) Add approximately 350 lbs. hafnium salicylate cake to reactor.

3) Agitate 30 minutes or until all cake is thoroughly broken up.

4) Filter. Slurry through No. 3 press.

5) When press is full, wash with 100 gallons wash solution

6) After washing, dry press with air, break it down and collect cake. Store

the cake in clean wooden drums.

7) Remove the drum from the pit, weigh and label them, and enter them in the

log book. Take them to proper storage area.


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