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oj

I R. I. 3525 JUNE 1940

UNITED STATES
DEPARTMENT OF THE INTERIOR
HAROLD L. ICKES, SECRETARY

BUREAU OF MINES
R. R. SAYERS, ACTING DIRECTOR

REPORT OF INVESTIGATIONS

PROGRESS REPORTS - METALLURGICAL DIVISION

I 40. BENEFICIATION OF BORON MINERALS

BENEFICIATION OF BORON MINl,RALS BY FL..OTATtON AS BORIC ACID,

BY R. G. KNICKERBOCKER AND F. K. SHELTON
PRODUCTION OF CALCIUM BORA 1 E FROM COLl.MANITE BY CARBONIC
ACID LEACH, BY R. G. KNICKERBOCKER,
A. L. FoX. AND L. A. YERKES

,
I

I
AFTER THIS REPORT HAS SERVED YOUR PURPOSE AND IF YOU HAVE NO FURTHER NEED FOR IT. PLEASE RETURN IT TO
THE BUREAU OF MINES. USING THE OFFICIAL MAILING LABEL ON THE INSIDE OF THE BACK COVER.
I R. I. 3525,
Jl::.le 1940 .

REPO R~ o~ I~j"VESTI GAT IONS

m~I'rED STA~ E S DE?AR::i.l}~}TT OF THE I NTERI OR - BUREA.U OF HNES

~--'======;=:::=::.:=======-==========:=================================

PROG~ SS RE?OR~ S - METALLURGICAL DIV!SIONl/

40. B 'n f3f i~ia ti on of B~ r on Li n(' rals

FOF-" O:a.D

~le Meta llurgi ca l Div 23\On i s continuin b it s pr ac tic e of r e.po r t-

ing the r Cl su}.ts of lab o r[lto r~r \IIor}p r om, tly i:1. the f or m of p ro [;!'ess repo rt:.;

in \·,hi ch a re g rouped ra:9c r s co v e ring 0 r k on relate d sub ~ e ct. The p r e sen t

r eport c ove r inv os ti ~D t i a n n 0) th0 b enof i ci atio n 8n i ut~:i2 atiQn of boron

r:i n er,1.1 s occur r ing in t h e' \ofC's t :) l'n pa r t 01 t he Un it ed Sta t

I R. S. Dean ,
Chicf :En inee r ,
M~tn. l1ur r · ca l Di v sion .

CON'11EN~S
Fa e

B enef ici ~ t ionof ~oron ~in era la by Flo t ~t ion a s BG r~c Acid, b~
R. G. Kn i cker"boclre r, and F . L. Shelton ......................... 3
Pro duct ion of C-:. lciu:TI Bo:' t o fl'o:n Cole!Ilal1it t' 'o ~ r Crt "ooniG Acid Le.:J.ch ,
by R . G. [ni cker'oo cker , . L . Fox , r,. nd L. A. Ye l'ke s ............ 13

y The :3nreal: of Mir:es o,1 i ll \I!elcou)A r epl'intinb tJf t:ds paper, pr vi ded t h e
follo winG footrJ.J~e rtcknowloc gmen t is u sed : " R()p~ in t ec1 from U. S. Bur oau

I of Mi n e ~ :1er;>ort of Invest i eat i ons ~S 25 . 11

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 BEIXFICIATION OF 30FDN I.IImALS 3Y IZOTATIOT A S ??OIIIC ACID

The E l e c t r o r n e t a l ~ . 1 ~ ~ 1 Tc ,~: t.tl3 1 ~ t n ~ i r of t h e Bureau of Miner,, 3 o u l d e r

C i t y , !.Tev. , i n v s s t : ' . ~ : e s 1 : h .-inc.z-.l ci.c;,oritr, i n 51-3 r e g o n around Boulder
Dam, i ~ d t. h i s papei- ? i * e s m t ; tvr) cl-c~;ef.o!~~ilcinl;$ of n s 5 s i q n of atufiies on
boron n i n e r a l a G B ~ O3;;tlir t ~t;s?,Lo::.

Thn b o r n t a de-nosit s of Cnl-if?rni-:l .qacl i:r-~ada i n t h e r e c i o n around

a Bou!.dsr Dnm n r e of ti-,:-ee t:;?us: ( I ) Sc7:urzf;cd 3rir.c an4 mixed cr::stcllino
d e ~ o stia , as e x ~ m p l ilfe d by Sc . ~ r l c s:?kc; ( 2 ) f a i rlp puro c r y s t a l l i n o
sodium borat;! t z p e s , such as t ; ~ o s oo: tilr iiralnar + i s f r i c t , Calif o r n i u ; untl
(3) c.11ciu.m bornto deuos-it 3, f o r o::am;,lc, t1.c c o l c m u ~ i3t d z p o s i t s of C l a r k
Co-mty, Ycv. Figarc 1 i s a p h o t o ~ a ? b -01 tlle V e s t %id C ~ O I J I CCO. ~
property.

I n t y c ~ i x t i c : ' , ::cvcnties, m d s ~ . r l : r ei&L+.?ec, icrn.:: ?-id u1e:cite from

~arzherazd l a k c m d r , wel-e t h e r ? = ~ i er,o.,rcen, f of bo1.0~1rnj-ne~als. biice&
colcrnanite o r e Gis!jl.nce4 thcco cboi.lt 3.837 w d : . n s tnc: p r i n c i p a l source
u n t i l nbout 1575, vk;?n t h c C O ~ C ~ U ?bor2.tc?I p e r i o d ~:c19 rn';her ri3ruptly c l o s e d
by bokh t h e S e n r l o s L P ~ pOr o j e c t nil dhs discovery o f thc! I:cm County
(Cali:. ) d q o s i t s of k e r ~ i t i !ar.d >or?.- these opcne.3 t h e s o d i m % o r a t e
9
8 p e r i o d , w!:ich e x t e n d s t o t h e p ~ c s c n t .

A c k n ~ w l c d ~ te n

The autho-s t b ~ n ' : t\c T'!est f i d Chenicsl Co., E. F. E a i l n e r s , gcneral

m 2 e r i n t c n d z n t , me J'. !I. *;Jilsnn, Las V c ~ z Yev. , , f o r -pravid?.ng f o r o u r
use a 7 3 - u c o o f tho c o l e x ~ l i t eorr! s.mnlcs; mi! ?hc Amc~icnl:Potrtsh d
Chemical C o r p o r t t i o n imc? I..'. A . C - G e , d i r e c t o r cf r e z c a r c h , f o - camples o f
S w i - l n s L&e s z l t 3 a>C >:in0 c0ntainir.g boron r;:incrnls.

They also pr&tch~ll:.rac.knrll~lcdg! th.o a i d given thorn during t h e work

by !?. E. Cod.y, P. E. ? c r i y , an3 P. 3. C h ~ ~ e h \ + ~ol'~ rth?
d , 3'?octromctnllurgical
..
L a b o r n t o r i c s of th:. P c r ~ ) a ucf . . i ~ ; . e .

Actiaii s q e r v i cine e q k i s c e r , E l e c t r o m c t a l l i l r g i c a I S e c t i o n , E i e t a l l u r g i c a l
3!vir,ion, Oureau of ijli'les. .
J u n i o r chemical enfl!ieer, 3 l e c t , r o r 1 e t n I l u r g 5 c a l S e c t i o n , t ~ ! o t c l l u r g i c n l
Divi3ion. 3 c r e e u n f 1 : i n ~ s .
S c h a l l e r , :i. T., I r X l u ~ t ~ i N
a li n e r c l s and Rocks ( i ~ o n m e t a l l i c s ) : chap. 8:
Tiorax and 3orntor,: Am; Iast. l.;i.rz. and .Met. 3nC. , 19:7, pn. 149-152
-3-
R.I~ 3525
Gen~ral Discus sion

The process de 'crib ed ho ~e co~ri ses th f or tion of boric a cid from

I
the bo r on minerals in ores and it guose ~\ent separa tion f r om the gangue
mat ri ls by flota.tion. The di gra tic flow "he et sho"m in figure 2
outlines the pro ce 3 . The f . ottion of boric acid h. s b een reported
previou~ l y ,5..1 and the r emaining st op s a re not a.ll n e\'l; howevor, \'19 beJli eve
tha t th combination of s tep ~ i s ori ginal .

)301'1c a cid in solution i g r(' l ea~ ed ~ rom its ca lc l um and sodium ~alts
by acids a s \fea.!c a car bo nic,2J c nd f r ee "' olld boric a ci d i 9 rel ea sed by
acid s only sli ghtly stronge r .II ~fuere solid boric ac id i _or ed , t h r-
mo dynamical ly thA r eaction between the bora te salt ~.d the ac id will be
complet in a gi ~en volum e s06~ent, provi de e ou a cid is added.
Sulfuric a ci d d sulfur io: id~ re t 10 i nexpen sive sources of a ci
available f or the reducti on of f r e soli d bo ric aci d . Although this paper
is devo ted p ri marily t o ~ o lG man i te or e th mcthod roe been app lid on
oOl •

'boron :niner a l s from So rl es ak(3 Its and s boell f ound to be equally

effectiv e .

Boric acid i s u "natur 111 l ontin . mat I) i a • ' roth e~ ~ E'. lone having bcon
roport od 'D r .viousl DoS reinc; ecoe o.:ry f or i +- 9 r ecovcr y;.21 this apor ro orts
its f l otation wit hout t \o add i tio of r gonts . Bori c a cid f lo t s almost
too re:1.d.il~r. The f r oth , i 1 t he bsenco of cert i depre ssants, is so heavily
l Rden with the acid as t o r eq i r t wo or mor clean i ngs t o f ree it of
entr ined ~ngue t er i als . Pi r 3 i s a photo gr ph of the froth. Clay
and . . hale r e int ermixed \.ri t h the bor ic ac id, t ogether i th a F1ma. l l per-
I
oentag9 of t he r ea ct i on sal ts . _O leve~ , a product 0 ~ore than 90 perc ent
boric-a cid wi th an over-a l l ree o ery r eat r t n . l' :,Jorce. t can 'oe obt a ined
rea ily by using a colomanit o or of 1 ss t 2 - . 0rcc~ t ]203 gr ade.

The flotation of boric a cid \I]i thout r ea ont canno t ~:)O oxPlained
easily. A!dr eva an Kuz ir.. ir t r o ort u t is. §} 'I'~n unuroa t c d ore usod
ha s no frothin g :properti os . T. e boric cid formod i n so ti n by either
sulfuric or sulfurou s c i o. £ f rom b O l to p r oaont o f r at ine properties of
equal va lu ; cheM ic ~ l ly p U'C bori c ci d f l o ts r oadi l , 99 . 5 percen t of a
-65-mesh sampl o a s 10 t ed i one xpo rimcn t. or ic ci d f ormed from pure
bora..;: by sul fur di o "i de r O(1ui r ed vory C'!mal l NIloun t '" of f ro thor for its
co mpl et e r ocovcry i t h'" f ir st t ost , lt t h . . r eei cui t ed b~ln 0 imp r oved in
frothin cap ci t y t hr o -hout t hroe con ocuti v t oat s i'ithout a.dditiona l

51 Kn st r, J., Kni or ·ooe c r, R. G., FQ x, A. 1., and Porry , P. R., Recovery

of Po tnss iwn Su~fate ~d Al umi nn f rom A it o by Fusion ith Boric Acid:
Bur eau of iL'~e s Rap t . of I nvc ti t i ona 3438 , 1539, ~ . 10-11.
~ Bur or, Alf r ed , Process or Pr od t on of Bor ic Acid: U. S, Pa tent
1,108,129, Augus t 25 , 1914.
V '~inkler, J .• Fa cto r s i n B r ic Aci d I· anufac tur o : J ou r . A Chern. Soc.
11. I

vol. 29 , 1907, p . 13 ~ 1371.

~I Androeva, A.I., and Kuzi n , S.A., Flota tion 0 ~or i c Acid d Borax
f r om tho Produc ts of tho T re~ t mcn t of I ~ . r a ~ orac i t 8 : Ap. l. Chern. ,
(U. S.S,R.). vol. 10, 1937, pp . 345-52.
7680 - ~~ -
I

De pressants ( op ti o nal)

I
So I u ti on

Sa tur a ted H3B0 3

so I uti on

I Figure 2.- La borat o ry f lo w sheet, co l emanlte ores.

• • •

F i g ure 3.- Ch aracteris t ic froth o f reagentles s flotatio n of bori c ac id .

 ~.I. 35"5
I f rother s . Contami na t ion of t h e cell \ s checked r epea t edly and found
negligib l.J , Boric a ci d formed . from cRlcined colemanite f loat s s readily
a s that fr om the r a ore . :Boric d.c i d f orn;ed f rom r a '<'l Sear le Lake sal te
floa ts r eadily wit hout reagen ts . Te ep l e~ bri efl y discur- se s contami na t i on
of Sear l es Lak e bri ne by f r ot-her s de r iv ed fro m dese r t plan t G. The bo ric
a c id f or:ned f ro m c ol eman i te is f l oated i n t he treatment t a nk b~r the excess
S02 , and this ha s possibi l i t ies u s an i ndu st r i a l separ ation . ~hi 8 f lotnti on
a lso occurs throu gh t n.e decompos i ti on of carbonates by ~ S04 in the f or ma-
t i on 0..: Do ric 13.cid by H2 S04 from b orat e or eG cont a inino ca rbonat es .

Th f lot a tion medium , of cours e , is a sa turated bri e , ha ldin bo ric

ac i d and va r ious o ther sa I t o i n s o lut i o~ . Byp ro duc t s have no t been in-
vest i ga ted; ho wever. sodium ulf i t e a nd cal c i um sulfi t e are p r Od\lC ed from
the sodi um an d cal ci um bor a t es , r e8p e ctiv el~. i n the sulfurou s acid treat -
ment ; f ur t hei."' work would be req 'Jr d t o )rov e thL.l a valuable fsatu!'s of
t he proce s .

The proc e ss has been a:!!plie d on four t ypes of :!late r i al ~: (1) C lc i ned
And cre enod c ol eman i t e 01'8 ( t:l0 usual metho d of <foncen tra t i an);1QJ
( 2 ) ca l ame_ni t a or e c o. centratcd by el t J.'iat ion ;!1J ( 3 ) raw mi ne-run col emani te
ore ; and (4) Sear l es Lake salt . ch t .. rpe has c Grta in advant a ge s , but
a ccordi ng to expe ri lr.ent al da ta th f ir s t t w mat erials ,..ppea r to be pr eferabl e
·Jhen sulfu ri c aci d i s usee. ; the Sea rlG Lako salt!3 and. ra. I coleman! te are
yi eld sub t an ti ully equal r ocoveri e ii t h the sulfur- di oxide tr e t ment. By
t hi s metho d , boric ac i d in prod.uced f ro;!) low- grade mate r i a l " analy zin l es"',

I than 20 p ~ rc ent B 0 "

2 3
Su fur Dioxido Treatment

I n tr en t i ng col oman i te orcs 'v11 t h <:!'.1lfur di oxi do , theso fac t or s wero

i nvestiga t ed : (1) Effec t of bor i c aci d medi um on format i on of and flo t a ti on
of boric ac id ; (2 ) ef~ect O~ ~trticle slz e on duration of ~s treatment ;
(3) effec t of va ri ous depressants on t he flo t at i on conc~ nt r ta s .
The fi r s t ma t t er investiGOted concerned the effec t of the use of a
sat urated bo r ic acid medium upon the f ormation of ~1d f lotat ion of boric
a cid . That the f ormation o~ .boric acid i n a saturated bori c me i um i s
feasib l e and t hat the boric aci ~ ~o for med i s r ecove~able y f l otat i on arG
demons tra t ed by t h~ data i tables 1 .nd 2 . The flotation medium a ten t 105
\oJaS dist illod '.'/at er :md of test 10'9 HUS a Go l t i on f r om tho ravi ou s to t
hol di ng 80 . 6 grams of B20 i n f;olut i on , s boric ac i d ( this appr oac!lcc cl osod-
3
c i rcui t condi t i ons n ocesrmr~,- in ori na flo t ... t i on ) . . ~~o flot~t i f) n r an cnt
we r e u o e~ i n eithe r tes t. CreG pr vi ou 1y co ncent r ated by elrt r i ation woro
used hc re , so t abl e 5pr eaents t!:i9 trl.!er economi c'" of. the process . In each
in s t ance , 400 er ams of - 150-mech or e ~as t r eat ed by 50 2 in 1, 00 milliliter
of medium f or 16 hours , the who le wa~ placed in a flotation cell and di l uted
to 2 . 500 millili t er s anCl. a fl otation t es t a3 comple ted .
I

~7 Tearle . J . E.• ~_e I n~~striul Developmen t

Che:n . Soc . lonogr ph 49. C em. Ca t .· Co ., New Yor. ,

I 10/See p. 1367 of footnote 7.

ITICcnme l l, G. A., end Rasor, J . P •• Procas s f or Removing Shale f r om a.
Ma t urally Occurri ng Borate : U.S. Pat n t 2.155 .784 , April 25 . 1939.
76m - 5-
R. I. 3525
TAJ3LE 1. - flotation of boric :ri thou t rea.gan t s
I
in -
Te st
, Ta ils
10 5· . 2 , 07 G.o
10 .• 1. r.4 2. :1

TABLE 2. - Effe ct of sa.t urat ed H 03 solut-4on " on f lot o.t ion of H3B03

Te st
Gra ms B-=03 in - I Percent H3B03 in
Conc entra t aG 1'('\ i 1s Sub. t ~on eonccnt r a t e
105· • 61 ~.•9 ~ L2 55.5 B~ . ~
109 .• 124. 6 ) .4 7..,. · 3 ~S
u c

Table 1 pre sen ts p r oof th t bori c ci c be conc en r a t ed by flot a tion

\.'ithout r eagents; t bl e 2 shO \'1e th~t ori c cid can b e pro uc ed in a ~.a tu.rated
boric a c i d me ium by S02, and tha t t h i rr~BO ir r e~ o v e rab l e in the f lotation
concent r t e a The conc ent ~a t e s lere not cle ned i n ei the r te ot.

Rol a tion ship of tro t ment t i me to parti clG i z

and mine-run ore . r especti vely , i s ho rn in t a 1 s 3 and
: or both elutriated
In a ll insta nces
I
tr.e 00 2 wa s bubbl e t hr o 1 the s of or o hal in spenBion in 2 .5 time s
i t B D"nss of H3B0 3 b r i a i:1e d i wn f or t he ti m~ g ' v en , nd t h i s r eactan t pulp
wa s pla c ed in t ho flo t at ion c el l , dilu t ed to ::'l. 5- per c sl1 t pulp r a tio by more
brine , a nd a flota tion t e nt c o , l ot

TABLE 3· - Re lation sh i~ of tr ea t ment time to A. rticle si zo l elutria t cd or e

M.e sh P tot"-:l..1
Test
of feed t,,'lils
116 .. - 20 31 . d3
117· • -3 5 31 . 83
118 .. -65 31. ~3
121 .. -65 31. 83
125 · . -65 31.25
13a·
1 ...
. - 65
-1 0
}1 .00
"7 1.00
Y
other t es t

I
- h -
 R.I. 3525

I '.2ABLE 1~. - t o pa rt i cle ,5 7.~min e -run or ~

T ,st Me sh Aaa1y rd ;.j ,h0"7d!=> I T1; "e of Ta i J. a"1U..v ', PI9 l'c ent of tp t a l
p !=' rcp.n t Il2~ &tmcn t, ~
t r hourr. .t' e r : en t, 3~,..Ol.J '~,003 i n t a i l s
.-- ---r---- ----.
I

132 .• 1~ • .)7 '"> ~ . O~

136 .. 15 . 67 1 3· 27
1"7,7 •• 1: . b7 l/? ~ . 61
143 .. 15. f;"j' I ll? 1£+ . 04
1 4 .. • 'j~ 1 4. 4}
From the d::t ta of t a 'J1e ~l 3 Rnd l: i t appearfJ tlw. t - ':>O-m IJ h ore r equi r e e
24 hO\L:'C I tl" oatmen ' ~, -3,5-~esr- '&' (\ qulr er. 2 to 4 hour s': nrl - 65- ~e £~'1 r e Clu 1rc s
1 t o 2 hour s I : d fi nor c:rindi~1g ~~ l" O ~.)a t :!.y i r' "J.nncce ... :~;r . Ecm c o , 'vI e
t he pulo r ::lt i o of 2. 0 to 1 , - lj :=;- 11P.S" 1 or<=' t nnd 2 hou rs '
a.dop t ~d ::LS s t ll.:ldar d
tr eatment wi h 802 &as , fa l oi>!ed by flot at i on a t u pu_p r a ti o of G. 25 ·t ~ 1 .
Thi B r &d.tment cave c:! 1.ti d'a. cto~ :!oOK t'" i llngc in t !, 1 l at er t . ~tc . A fe~r
taiJ_inc s f'...na !y scs : ollow ( hGCl.d. aJ"!3. ys i s , 19 . 53 percent B20 ):
3
TABL:iTI S. - P ro..££s:-· e?'fic iency on mi no-mn col€'~i t(J~

Test GTni 1s ~ssny , P e ~c cnt o· t ot~ l COrl e en trn.t i on

p erc ent, B~O ~ ]203 ia t ails r a ti o
------~~----~----~~-------------+---------------------

I jJi.Q. .
146 . .
49..
150 . .
1T2 • I?
- 1. . 7 1~
2 . 50
2 . 15
5· 6
1? · 3
?. 56
2. 36
2 . 6t~
5· 9
153 ·· 2. 37 ; .2 2. B5
15l ~ . . ? . 14 9·~ 2· 33
15 . . ? 19 EL5 2. B6
~ ; _ .ll ~ ° .0 2 . ~9
11 Residue .

Th~ con ai 3t cnt ya 1uc for t ho t a i 1i n g c-, analysis of ]21) ~ i B apparent..

Two e:"'' 'P l anat iouA CFl n be .~dv~~ C;;') d : 1 . Entra inmc,1t 01' 'bol~ ie a c i d in the
ga.l1gtl . Andre6va n.n d Ku zinW .dvan e th i:; thcsi ~ ; th "r I so ment i on GU -
t inment of gM guO i n t:le conCE'!l tratfl . 2 . T . . . e tai i~1 ~ S ~.r e wet wi th a
sa t ura ted bc •.' i c acid soLltion , ':'hi 1 , u pon _ry n , g v e::; til i l3 consisten t
va lue of ab:.>ut 2 .1 nercen t 3?O~ . ':: ef\t 140 , anl~ lyn i n of a l'esicue f rom the
rec ry ctal llzation co nr:entro.tl.on of a uori e o.cicl flota t i on con centrate
(descri be d more fuJ.l.f i n cO;J.nec t i 'ln :i t~l t n.ole 7, l? 9), i ~ i nc lud ed i n
t ab le 5. By corr.pa ~·i sCJn ~'j t_ . the flotation ta.l,l i n~s , i t i s S 9 n that thi s
exp l 8..l1D.t ion i s perha,?3 the betl;e r . r:'bat t:1j. S exp l anC;.t ion is true i s shown
fuxt her by t es t 133 I table 3 i n '''hi eh the t(~ ili ng ',.ras tho r oughl wa shed vi t h
\..rate r, r oduc ing the tH.il_n6 ann1y. is to 0 . :;1 ",o r ent B2 C3' In p rac tice ,
di solving out thi s bo ri c a ~ id i th 1a ter 11sed to roplonl ~ h t he f 1otat io
ci rcui t '{ou l d b e ve :.c~ 0('0 11 mi cn l .

12/ Andreova, A. I., and Ku~in , C. A., \vor' cit od i n foo t not
I 76so - 7-
8.
R.I. 3525
T b l e 5 alao S:tO"/ S pe rcentage of t he t ota l 132°3
The avora e of t he seven t os t s given is S. crcent.
lost in the tailin s . I
Cloani ng FIotation ~ Cenc on t rato~

The cone tr ~ltou o'ut ain d fJ.'·om t h (;) mL fJ -run ore WeJ-m oonta.min~te.d. \'lith
c lay . cfllcium sulf i to , c.... l ciurn 9U fate , 8Jld v riou et __ s r m t e ri a ls. Two
mothods of tr o·.t i n C thoRe con contra t oo \vore i nVG Dt i ga ted,: (1) D prosn ion
o tho con t e-min t s in oi t __or or bot the rougher and cleanor c o l s of tho
f l t u ti or.. circuit; ( 2 ) eC!"Ystal 11z _ti on of the H"):B03 conc entratE). In
prnctic e , a coobl nat ion of those is to be 0 oct a. As the ~- of the f lota-
tion ci r cuit i s l e ss t h n ) . 5 , t , pr ot ct ive colloid and n ~u tTal mine r a l
salt s ar e th e de 1' e san t fJ mo s t li l"::el~r to b e effoc ti~!e.

As boric Rei d i q e~ i • ~l o nt e d , t h e au t horo confined themse lves to

att emp to to d ep re os the i,:.a ngue mater i al0 . Tabl e 6 pr e5€':lt s di gs. t of the
da t a on de-preS38.nt "' : All ores ere t r Gf.l.t e by t he standarCi.lzed pro cedure;
oro s in t ::;ts . 32 to ]4 + a s say d 15. 67 . ar cent J3c:.0 3 ~ t:to ec in t e st3 11~ 8 to
163 , 19.53 p~ rc ent B?03'
TABLE - Ef!:(i c_ of deprc s~ conc en trate- grade

Q:ua,n: t ity, Pe rc ent :92°3

Toot b e~rc..: t Poin t ~
d ed Ib·iT clean ed con-
133·· ......
1~ 2 ........
Non e
starch Roughe r I-J'{4
can tra"to
,1·5
48.38
I
144 .......• 0.0. 1st cl .. er 1/ ,- 45. 46
139 .. · .... " e.o. do . 14
2d cleaner
, I,Lt 49 .42
laOe........ Gl u e Ro' h J.' 1~{~4 48.31
1 ........ do . l r- t 1 p,.n r -1./ 46.29
152 ........ Gum a rabi c Ro he r l-l/~~ 49 . 48
'~/C~ 51.36
153 ·· -.... · Q,uebracho extrac t do .
156 ........ no. 1st c "an al" 51 ·71
162 ........ Corn sxt.rine Roti.gne r 1-1/4 47. 56
163 ··· ..... Na2 S iO~ no . 1- 1/l~ 47. 96
159·· ...... Quebracho xtra t ao . 1-1 /}~ 50 . 24
CuS04 o. 1
166 .•...... Que racho extr ct do. 1-1/4 49. 48
All') ( SOlt ) 3 1-1/4
167 ........ Q;uebracho e:v:: tr.'l.ct 1-1/4 . 50.18
euso 1 2
From t ab le 6, it i ' oeen t t ~' u . rch. d07 t rine , gum raoie, and
q ~ebra cho extra ct r e dAp r s . nnto fo r th g e mat ria l i n the coneen-
tra t e a nd t hat quebracho Axt '''act i ~ pe r hapc th bes t . As i s usu.a l l y the
case the qucb r ncho c n t nt mua t 1e r i g orou IJ co trol l Copper and
alumir.um C': u lfJltes help t o co n ~l"o l t e frot in t endencies of t he bo ric a. cid
(t h i also i ndicates t t t a fl"othin is n ot duo to o rgo.nic contaminan ts);
I
 R.I. 3525
I 1-1/4 pound~ p r ton of e i t her of t hese sa lt ~ virt ually destroys the froth
an the addi ti on of mo'.·m fr'o thors becomes necessary .

To obt ai n £l1me s t chC'mica 11y puro bo r ic a i d , r ccr: r s tal1 ' za t i on fr om

ho t solut i onc prov ·8 satisfc..ctory . Saturated so utions of bori c ac id con- , /
t a i n l.j.g Grarn tl pa r 1, 000 gr ams of sol u t i on a t 20° C. a.nu 28 7 gr am. at 100 0 C.2J.J
By treat i ng t h o fl ot<. t i on con ~ €Jn trate9 in enough hot sol uti on ( satur t od
wi th H~BO.3 ' 20 ° C) t o di s so I v c t.110 H~B03 ' fi 1 t:cri ng off tho W1d. i S 01 vod
materi a l , ELUd coo1in5 the solut i on , '- e recipi t ated a h i gh. grade baric ' acic~­
concen tra t e . Data in t abl e 7 p resent t h e se r esul ts . (Tes t s 138 and 140 are
on the concen trat es f r om the S02 treatment, and tes t I tl-1 up on t he conc n-
t r a te s obt ined fro m the H2SO4 t~Gat men t desc r i bed l a t e r).

TABLE 7. - Eff ic i ency of rocry t lli z ti on of H3B03 c on c c n t r a t 8s

] 2C3 i n head , H3~3 in co ncen tra t e , ? ercent of tota l ]20 3

TO ut
ner CBn t per cent i n conc ent r a te

l aS .. · a7 . 60 1/100 . 7 £1 82 .4
1 0 ... '7· 18 99 . 9 9S . 44
141 ... 47. 82 100 .0 90 . 61
II l lho bor i c aci d fa "" sl i ght l y dehydrn t ed.
?J Tai1L1 ~s no t r u-troatcd ; at c ro. :L'e-tr8atOc. tuice .

I P recau t ion ::; we re ta!~cn to prev en t dehyd r a t i on of the bo ric a c i d f ormed .

Tho fir st t e~ t g iven had 0 . 11 por con t water -insol uble materi al and 0 . 2
porce...l'l t Ca D. no othor i mpuri ti cs we r o do t dc t od .

The C i ef con t ami . t 0 the flotat ion concontrate i s a b or bed \"rato r .

This las deto r mine d anal vt i ally by ~ a ting a t 70° c~ sinco G. orz report
no -!a t c r is los t ·oy coric n_ i d at t his tempe r a ture . ill Ta bl e g gives data
on t h ' s :

Test B 0 ( concentrate ) ,
2 3
pe rc ent
I H20pea rc
t 700 C'f
en t
lCUl f'ot ea H3E03' Tota l,
porcen t n ercent
111 . .• 49 . S2 24 .03 7G .O IlI I Do . 03
112 . • 44 . ~4 ?o . ?O 78. 7 98 . 9
11 Bor ic acid li Ght l y de~ydr~tcd ,

Sulfur nd en. ci um oxi de in combined form and some cl~v con taminate the
f lotat ion concentr,".te3 . ~ hJ Eulfur is p r esent as c:-ulfi tes and sulfates
( the ln t t c r partly t h-"ouGh xidat'ion f- sulf i te s ). Ta'-;:>lc g i ' es th r e e such
concentrates (Ca O and S01 t cLlculuted to C~ S04 and CaS03 , B20 3 t o 3BD3
fo -. t otals'): .

I 7680 - 9 -
R. I. ~5~5

TABLE 9. - Constituents of li3B03 f1 ~ t a · ion concentrates

I
Te st Acid insolu"ule.
"f)e :ccent
156 .•• 51.71 ·50 0.23
157· .. 43.79 g.l .58
1 g •.. 1. 0 ~ .l

In two tests (Nos. 164 a n d 1 2 .7 4 and

5). the t o t e.l m.t1f ur pr e sent Has
2.11~ percent (these conc ent ra t s sayed 48 .8 .. ij ~rcent B20 and 50.0t~ per-
3
cent 132°3. re spectively). Calcu a t ed aD H3B03~ a nd Ca S03. 2H20. the se
account f or 100.15 and 9 9 . ~ 9 percent of the to t a ls, respe ctively. Thes e
concentra.t es had been d~i ed V e l" C r eful l - r
•

So m inve st i gat ion han a roo been made i nt o t e f 01'. ation of boric
acid y the 502 treatment of :Jo.lt mass s cont a.in ing bor ax and other alkali
borat es . T'.ese t es t indicate- t hat so i salt ", r a ct a do the c 1cium
s Its, and no new probl m developed.

Using the same procedure of 00 2 treat ment det ermi ned for the ca lciUlJ1
borate s for a reI t ivel hi~1 r de samp1 of dehydr t d'borax a ssaying
I
L!. • 80 perc ont :8 ° 4
2 3 , f lo ta.t ion concentrClt es as sayi ng 56.16, 55 .7 , and 55. 88
pe r cen t ,B203 wore ob t a i ned. The e correspond to 99 .7. 99 .1. and 99.4 pe r-
cen t boric a cid , respect i ve l y .

A sampl e of Sea rle Lake a lt, as shorn i n figure 4, obtained from

the Amer ican Pot u h Chemica l Co., Trona, Cnl i f " , w.lyzing 11. 20 percen t
B?O~. \'Ill. trea ted. Th e s olution wa. .aa tura t cd it h both t he suIt a nd boric
acia t t hi s soluti on was ga"'sod \..,1 t h 8° 2 . fo r va r y n b po riods of time (the
t est con t nnts wc r ~ 400 gr~~ s of salt in 1, 0 0 il 1i litor~ sa t.urnt d ~olution
f or troat mon t tmd flot ..... tion in 2 , 500 millili t er solution) f o llo ~ od by
f lout i ng the "boric a cid formo d . wi thout r eag,:m t . TanIo 10 vos tho data.
oot i ncd:

Test Mesh Time of tr ea t- Anal 81 pe r cen t :B 2 0 PArrent of total B20~

I

mant, h OUT 0 3
Concont ra te_ Ta ils Concentra te Ta ils
180 •.• -20 1-1/4 5 .54 2 . 80 96,,85 3.15
181 ..• -20 1/2 53 · 72 . 61 97·18 2 , 82
135 ·· . -35 1 50 . 82 2 ),-6 88 .20 11.80
186 ... -~'5 IJ: 53 . 81 ).. .01 ~4 .]g 5·22

!:'if Reported.
,
~~ellori
J, W'A I no r gan ic and Theore ti c 1 Chem. Lcngmana - Gre'm
Co .• London, vo . ~ I 1~29 , pp . ~ 2 -53. ~he r e fere ~ce appa r nt1y is fro~
Jour. pr al t. Chern •• vol. 59 . 18b6 , . 179.
I
7hBO - 'f) -
I

Figure 4.- Core-dri II samples l)f Searles' Lake salts. (Courtesy of American
Potash & Chemical Corporation.)

I
 R. I. 3525

I ,Fr om t he data p re ",en t ed , t~1e proc8£19 i s cleemed to b e ppl ic ble ·~ o

sodium a ~ \ve l l a s ca l cimn b0rRte '"' . As these te r. ts we. e made con s cutively
~i th r~ qi r cula t ed bri ne , we beli eve that the procos s c n be made continuoU3 .
Ku zinl~ d et.c rib e~ ~ ' p r ocec u f or the Bepara ti o n,g~ bora x d bor i c ac id f r om
t he Mi x ture of th e i r snI ts . Andreev and Ku zinht have f loa. ted bo 1c a. c i. d
f xom maen e . i~ sul fi t es and sulfa t e s d t h t he use . of S02 '

Suli1r i Ar. id Troat ment

Sulf uri C 8.c i dW can be ut i i zod i n place of 'mlfur ai oxi de whe n

d~si!,ao e . T ab ~ e 11 pre ..~ents the r enults of four t es te upon t he e1ut r i a t ed
c o1eman ' t e or e ~i th sulfur i c ac i d a s t he I eact 3n t.

TABLE 11 . - Eff i c iency of H2SO4 t rea t Mcnt

Tai ls
92.... 32 .3 7· 3
102 .... 34 .25 5.2
107 .··· 35. 5 53 .77 3.2
10 g. . . • ~ . 0g 1, • 0 .0
1 Con cer..t r a t e pa r tl~r dchyc'Lra ted .

I H2 SO4
In each instanc e , ' 0 IT£.:..010 of the olutriated or o wa~ , u~ed , a..'ld enough
3.S addod t o g i v ~ ind i catod ncid EJXc c .,S of tatlo 12 ( \~h ic- - O"i v c the
t es t facto rs ) in t h: 2 , ~oa m' llilitors of l ota ti on brine .

TABLE 12 . - Tp. t fac t ors in 2804 treatncnt

~er. t Exces s E2804 , gram~ pe r f/er-.h of Vo1UlJe of treat- Time of treatmen t I hour~,_
li t e r i n f lo tat i on cell feed r:1e!1 t s'J luti o:J. . ml Oold Heated
92 .• 43 . 6 - 20 500 24 0
102 •• 20 . 0 - 20 1 , 000 22 1- 1/ 2
107 .• 21 · 3 - 20 , 000 22 1 ~1/ 2
108 •• 18· 32 - 35 1 ,000
.-
13 l-I/?

157 Kuz in , S. A., A Flotation Procec~ f o r the Sopar a t i on of ~orax and BOl ie
Aei d f ro m Mi xt11.re of the ir Salt J our . Chern . I nd . ( 09 C O\t/) , vo 1 . 12
1935 , p~ . 277- 279-
Yi/ Andreev , A. I ., Dnd K i n , S. A. I wor k cit ed i n fo otnot e g (p . 4 )
ill1'fin:.::ler , J., work ci t ed i n footnote 7 ( p . ~) .

I 7680 - I; -
R.I. 3525
While. from a. the or tical viewpoint, sulfuric aci d i s a~ satisfactory
for the p roc es~ as i"" sulfW" dio xide, cer t a.in limit tion '" 'ere founrl to hold
I
to obta in re suIt s compnr ble ~'1 th the 50 2 t rea. tmen t. Briefly, they are:
1. ''lith mine-run or , t !1e sulfur ic acid at t ac ed the car" onates first, and
this virtually doubl ed th con uDlp tio·l 0: sulf _ ie a cid. .tTi th elutria ted
ore, 'cht; carbona t e s a r e vi rtually li nli ~ te a nd r c overie 3 t a in to ble 10 I
-ere achieved ith 95 to 100 p ercen t of the t or e tica.l amoun t of sulfuric
aci n O~9; <fd to :rea ct 1:lith the orat pr es t. 2. It was found nec es sa ry
to h t11ilall te s t s to obta i n results compa r ablo to tho se obta inad 1.i lthout
h a t in the 502 trG( tm n t.

C01omanito can be concent r ted by o lut ri e~ tio n (U.S. Pa tont 2,155,784),

since t. ho cl · y and !lalo in . tho r aw a r e aro nTllch f i ne r than is
tho colemani te
upon grindin thro h 10 to 20 mesh . Ta bl E) 13 p r o sen ts the rosu lts of one
test:

TA]LE 13- - Elutria tion concentr tion of colemanite ores

Hea d sa p Ie, - 200-m sh elutriated +200-mesh elutriated

j)ercen t slimes,. .,per-can t sa.n ds_~ · percent
B?O~ •••••. , ••.• 15.67 1· 92 26 . 22
III ~ luble s ..... 11. 93 27· 88 1~ .36
S03 (as 504) .• ' 7.95 .62 .82

Over a number of t es t ~ , it wa s found t ha t the data givBn in t a ble 14

hrld ~ore rigorously by elutriating ore as ying 15. 67 percent B203 leBs
I
careful l y at 200 mesh ilnd tha t t hese data are of mor e pr ctica l si gn ificance:

TABLE 14. - Elutria tion co~centratlon of coleman i te ores

Ore sample liB" lI ];tI

B20 3 , concentrate .. ,. p er c ~n t .31. G 34.~)

B20" limes.. . . . . . .. do. 8·37 7·30
As repo~ted in Report of Inve sti tion 3438,191 a pulp density of
about 15 percent was maintained in the ce l l i n a ll flota t ion te s ts recorded
in. this paper to minimize th for ma tion 0 m..q, tty froth. Copper sulfa.te
aIl d luminum sulfat e are of va lue in cant 'oling th natur e of this froth.
, .'

It bas been shO\'ffi t t it i s fans ible to c one entr t c boron minerals by

fir t trea ting thorn wi t h su l f ur dio:A.'i d o in soluti on or vii th sul f uric a cid
an d flo'J.t1 ng the boric acid s o' fO l~ed · from t ho on 10 matcri o.l s . 'lTi th

,
colGman it e ores rul d orax sal t , no . oa6~nt ocossa r y f or t he f lotation,
a lthough g gue dopro ~ t s a vo n cl e~a r cone ntr · to , Da t a a rc gi ven to
show the va~~ue of clutri tion i n t he conc cntl' . t i on of colomanito.

ill ~1ink1 or, J .• lJ/ork ci ted i footnote 7 (p . 4).

rlI Ko t a r, J. Knick c rbo cl{or, R. G" Fo:t , A. L., uno. Perry
I I P. R•• '1,"Jrk
ci t ed in f ootno to . (p . t~), pp . lO~J 1 .
7680 - 1
I

ClJ

o
u

>

-
CD

I
z::

CD

">

u....

,
 n. I. 3525

I PF:.O!)tjCT IO~T O~ CA.1CltJ1V. BORATE FROK ro4~iA.NIT BY C HIe !eID 1EACH

By R. C'. ' Y..ni·ckerbock e:· ,l.l A. · L. Fo"X ,gJ and

. L. A. Ye-,·kes..V ..

I :''IJ.otJCTION

Previou.s ·ork '01 t hi s la~or to ry on the pr ep rati on of calcium boride~

T

f or u s as a r.1etallurgic3.1 soxi iza r c.nd as an j. n~ermediate in t h e p repar a -

tion of boron and b 1'0 ;". rwrpoun . C i n . co te t l":3. t th~ c o'st of t h bo ric aci d
ur.ed a s a r aw mate r' a l ' 113.., · mJ.,~or it eJn in the t ota.l ..cost of t he product.
Ac ca lcium boo ate cul d b;; a ~ul t able;; r a r mat.c r i a l i n t·h 1.s , ro ces s, it '..vas
decided to 1 ~ves ti gatG i ts lJ'ndu ti froM color.:a n; tc , i t~o hop o 0_ 00-
t[~i . in~ a s uree of b0ri c dXic:e lesu B)..]?ens i -v-e th~l bo ri c ~Ciig , U ~e · c'ould
be found f or such mat eri al i n. t!-"lC ~ ielc: 01 cer mi c £"la zl) s ,.2/ S g l ss , and
as CL metal lur ,i eal flux . Fo:::' most or t hese uee s i t~ ui t a bility would
d pend rriT!larily on i t3 p:'''icc , and if i t cO"'J.ld b e r.1adA avai lable at a l owe r
cost pe r ur.i t of bori c oxi e than e ith~ r bor~x or ~or ic c in, i t !Quld find
a mar ke t h ch o'll d justify r eopeninG the colemani t c d ep o ~it ::; of thi s
a re - .

Co lenmn i te i a hydrat ed C~4 cium bor t e hari n th e ro mp o s i t ion

2 Ca O.3B20 3 .5H20 . I n_the lqrgG 3.11vi I e Wa;,h · ( Ne~:.) dep o si t, the mi~e -run

I or e '3 been l' c-po rt edlJ t o fl za 22 to 23 percen t bor ic oxi de . Howe fer
( larg &~rnp l e of nin~ -run or o taken from the West End Chemica l Co .
property analyzed onl y 17 .0 p er cent boric ox i de , and according t o the ·gene ra l
suporin tendent ' s ad~.~icc , th i s would bJ the compo s1 t i on of the min - run ore
I

ob t a i nab l e . Fit;ttre 5 i3 u. pho to~rapb. of this depoci t . The majo r gangue 81

consti tuen ts etr~ gypS1.uu . cl n.y , sh,').le , ime stone , me.gnesit e , and san ds t o ne • .=.i
A chemical anal~ sis of t . e ~ead s~ l e i s shown i ~ t ble 1.

]J Ac ti ng supe rv i s i ng en ginee r , Ele ctrometallul' gic~.l Sec t.i on , e t a.1 1urgi cal
Divisi on , Bureau of !. ' nes .
gj A sistan t chemi st , Burea~ of ~ines .
~ PhyGica l scien co a id , BUl'eau of Mines .
:J Ko s t er, J., ~ickerboc ~ er J Rt G., ~nd Fox , A. L., An E1cct ~ oly ti c Me thod
fo r the Production 01 Ca cium ~oride : x eau of Mi ~e9 Re t . of Inv stl-
~t ionE ~ 500 . 19~~J ~o pp .
5./ Frenc~ , ' . ., Col ~D'.a'l1 i to a3 a G ze l·~te:-ial : J Oll.r. Am. Ce r m. Soc .,
~ o l . 14 , 1931 , pp . 739-741 .
.§j Uses of Cole::IaI1 ... toe i n Pi:lk and i!a r non GL,:,-zes : Ceram I I nd ., Vol. 31,
Septe~be r 1938 , p . 42 . :
V Noole , L. F ., C olel1l['~ite i n Clark County , ~Tcv . n Con tributions t o Ec-
onomic Geology , 1922 , Part I, ietals a~d . on:net3.1s Excep t fuels , bY'
F. L. Ranso~e , G. R. ~ lsficld , and . E. F . Bur b~rd : Geo l . Survey
Bull. 735 ("0) ', 1923 , _. 38 . .
r/ Hm·J itt , D. F ., Calla£;han , Eugone , Moore , B. ., ';0 len , T. B., Rubeg ,
I 7680
~ .r . and. Schr oeder , \.,'. T ., .r~inerll l· Resources of the Regi on Ar'ound Bould-or
I

Dam: Geo l. S~rv ey Bull . 871 , 1936 , pp . 106-113.·

- 13 -
R. I. 3525 .
TABLE 1. - Ana lysis of mine-run co1 emanit o oro

Percent
I
I gn i tion 10 as •••••••••• "23 .8
] 2°3" ..... , ..... . 16.98
S102' ............ · 16. 29
A1 20
3 • ..•.••.••..• 1.59
Fe 20 3 · · · .. · · · · ... · . 60
Cao •••..•.....•... 21 .56
MgO ••••••••••••.•• 8.03
SO ••. " ••••..••..• t ~6

On being he ted to 500 0 to 550 0 C., col eman it loses 1t ~ wa ter of

crysta 11iz tion and dec r epi t a t es to a fi ne powder , a c quiring a t th e sam e
time a rea t 1y increased sol ubility in acid or a lka li e lea ching a gen t s .
This as forme rly the ba si of i ts concentrati on , the co r se ly crushed ors
bei ng c lcined an t hen scr eened to r emove t . e ove r i ze a &:;lomerated clay
and gan a t lea ving a concent ra t contai ning approximately 40 percent boric
oxi d . The concentrat e wa s the boiled with so di um c arbonat~ olution for
t he prep a r a t i on of bQ~ax or a s tr~~ t e wi th u lfuric a cid to obta in a '
boric cid ~o lution. ~1 J . li nkler1Q} ~eaks of an old Ger man method of
tre i ng calcium bor t e orcs , cO' si s tin of l oach with ca rbonic a cid to
p roduce a dilut e bo ri c ac i .solution , ~ d r ~~ C} very of t he boric a cig.. QY
vapo ration and Cl~ t lli zat ion . A. BUl~ ge r1lJ and Kelly nne Jone~
patented modification~ of thi s p rocess, consi s t ing of the u s e of ca rbon
dioxide under pr essure , w£ ich €!Jl.ve them mor e conc en tra ted so lution s ai' boric
a cid. All of these i ve sti ga t or we re int er at d i n recove 'ing the boric
oxide s boric acid araa alubl e alkali bora t • :n et _0 t hi purpose the
di sadvantage of the ca rbonic a cid each, that 1 , lov C01ce tra tion of boric
I
ac~ d obt i nable in the le ch solt.ti on . bas made t:ts ::n'oco econo~ical.
Howeve· , i f t h boric oxide were to b r eCQV O d as cal i wn bor a tr. by prc-
cipi t a t i on fro m dilute O- olu ti on \or! th li me . t he 10\'1 CO:lCC!1.t r o. t ion of the
boric cid so lution oul d be of l e ss i mpor tanc : and if , i n a ddition, tho
source of t he carbon di oxide ,:,or e \O[B.ste produc t, such a l imo -i In 9tn ck
ga s . whi ch i 9 a va ilabl e i n t 0 :Soul or Dam a.t a , t ho p ... oco se S lou1d ·00
c ompe t i tiv ~ with ot. or bora t e p r oclJssos .

Carbon dioxid is no\'l b L·g obt a ~ ~qd direc tly from lime-
stone b Fro zen Ca r"o·onic· Co rpora tion ,ll' Nevill e I eland I
Pi tt sbur' , Pa ., u s i n ' an i npr oved Gi l l e tt e p roce s s. Ca1cin.a-
t i on i s ccorrrp l i shed in ch y that the ca rbon diox ide
'ob tai ned from the s t one is uncontami nat by e1 s . It M

i s cla i med 'hat t he p ro d~c t of t h i s plant 1s 98 pe r cent puro

and i s od or1 e ss and co lor le s s . L me i s a bypr,o duc.t.
§] San t myers, R. I·., Bor o!l a.nd Its Co mp ound: BtU'eau of idnes Inf. Circ.
6499 . 1931, 37 pp .
!QjWinkl er, J .• Fact or o i n Bori~ AciQ Manufactur o: J our . A~. Ch ern . Soc' l
vol. 2.:1. 1907, pp . 136 1 ~ 7~ ..
!lIlhlrgor, A., Pr oc s f or t he Production of ::So'r ic Acid : U. S. Pa.t ent
1,108,129.
WKelly, A. A., a!l Joncs , B. D" P;coces or the Pr epa ra tion of Alkali
. Pe taberat es Direct from oro Or s : Bri .l. i sh Pa to t 158 ,992 . February
19 1 . ,
WTyl er, Paul M., and BO\frl 0G , 01i \:Qr ronmet
Bur eau of I·~ in @ s Inf. Circ . 710 b ,_ i 27 iti0.!.
l ie ~a ncr Industri es in ,l939:
(7680)
I
I
CALCINED
.CONCENT RATES
LIME KILN
WASTE
CO 2
(LIME I<lU~ WASTE GAS ) GRIN D To
HEAT FOR
D EC!'!l80NATIHG
;:,uLU TION
I L IME

100 MESH

Ir
N o.1
LEACH TOWER

FI LTRATE

I
104-- - ' - ' F I L T RAT E t - -- - - - I

F ILT RATE .....- - - 1

Fig ure 6.- Flow she et of colemanlte pilot lea c hing pl nt .

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I

I ....o

La...

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I The r eac t ion oot ~/c cn car bon ic ac id and calcium borat e i s r ever sibl e ,
~rnc ee 4i n ga ccordi ng to the equati on :
R. I. 3525

~caO. 3320) + 2H2 C0 3 + 7E20 ~ 2CaC0 3 + 6H3303.

The p r o r e ... s of t he rea c tion \'J il l be a~ s i s t e (l by hi gh er partial pre sure
of C02t f ine rindin€; . £.U1 d l ong con tact be t ween . olid particle s a nd solu tion,
f01' t he ca c iurn bornte i e- on ly SlO\olly soluble in carbonic acid.

Ob j ect of t he I nve sti ga tion

The purpo"'e of thi~ i nve sti gat i on was to determine t he t otal r ecovery
of b ori c oxide by a carbonic-a c i d l each , t he effect of a ny i mpuri t'i s t ha t
might bu ild u~ in a cont inuou leachi ng circuit, and t he gr ade of calci um
bor a t e t hat would be ob t a ined by 'Orec ip lta.ti on \'lith l iIr e . The t es t via r utl
on calcined conc en tr t e o pr epur ed a s d e sc r i b ed above and obta i ned f r om the ol d
loa ding d epo t of t he W eGt End Chomi cal Co. n r La'" Vegas , Uev . Table 2
giv es the anal~· s i s of t he SOO- poun hea d sampl e used :

TABLE 2 . - Analysis of col eman i te concentrat e s

Concen t ra t e s Ca l cula tod to

a s used dry 'basis

I
_ . ----''--,., ----+---=:::..:;....:;;:..;;::..r-:i;...-.---+--~~~~;;..;;;...---

B20~ ...•.... " " 42 . 46 45.90

siCi············ 8. 57 9. 26
A120~ ........... 1 . 17 1 . 26
Fe203 ' .. .. . . .. . . . 49 • 53
CaO.... ......... 27.77 30 . 02
gO ...... ....... 4 . 20 4. 54
CO2 .... ......... 5.09 5· 50
so') ...... . .. .. .. 2.73 2. 95
E?O..... " .. .. •• By difference

Egaipmen t Used and Plan 0 Ope r a ti on

Fi curo 6 i s a flowshoe t of t he proposed 1 achin~ and prec i pitation

I process , and fi gur o 7 i s photogr aph of t:t!c pilot l eachi ng plan t. The
l cac~i g t ower s con~ i st cd of l 2- foo t l engths of 3- inch i ron pipe p l aced
v e rtic~ lly . The ' bot t om of cu ipe was c l osod off ith a p i po cap . through
which a hole had been dr i l l od fo r the cdmi ssion of C02 ' A grid , consiG i n
of ll. pIa to t ~ lr ough \'T hi ch many fi ne hole s had b80n dri l led , as \ aIded t o
the i nsi de 01 each c up to d i ffuco tho stream of ga s . A 1/2-inch feod p ipo ,
12- 1/2 f oet long and open o.t both cnds , · \'l9.8 suspondod i n cach t ovTOr . Tho
concentr teB and water \-Jor e fod i 1tO tho i nne r or fo ed t ubo and emorgod intc
t ho ma i n 'Go wer t 0. po i n.t. t '.-IO or thro ~ inchos f r om t ho bo t t om, \. honco t hoy
wore c r ri ed t o the ovo r~ loi noar tho top of tho tow~ r by the slo wl r isi ng
column 0 -" pul p . I n t h i B \.,~ th coar se r partic l cc ':Jh i ch r o o_u ir od a l ongor
I

t i me of contact i t h the loachi ng a.gent , woul d ri s o morc Blo \'Jly.

I
7680 - l~' -
R. I. 3525
The ga s used wa s ' c r:mune rcia l bottl ed. C02, a.dmi tted to the to\"rers throurh
the open ing in tho bott om cap.
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The aper.'=l.ttOll ~,a s c m t.ercurr ent. , e~n c l1trates being f ed i:.1.to No. 1
tm.,e r b~~ m s of a. dry n:a c ' l ieal fe edor ~ t the d esi r e rate, togethe r
,·Ii th l e.:lch li q or f ro m .Te . 2 t o\,I ' r t '.IJ .i c ': ~ a 1 80 fe d i'!l a t a controlled
r at e by means of D. s i ph n. T ~e ov :-:f l ow : ro:n No . 1 to\rJer \I/!LS f il te r e d,
tho fi lt r ato go i ne; to t e . r ec 1T) · tat io ~1 ta ,·hile the soJi1 \'Jent ba ck to
No. 2 , the seA. en . . · to \'Jer, f or- :L ina l ~trt:1 c t :'o n 01 it ... bor ic o:v-ide. The
li qu or f or th scav ger t o\' 91' wa tho li qu or obt inecl fro m tho
preeip i t a tion t ank I' t er r enova 1 of t h bo r~ t , W L..i ch wa r ec overed
0 :1 a fil t e r. Th e 0 rf ow Leo rn 4- he sc t owor \.,ras aJ. 0 f i l ter i,
t he l't' siclue b ei~g d i . . cardec! n il t .. .i l in . ,tI.l il J t: , pa r tly satuI:t.t€d liouor
wen t to No . 1 to \Olcr to t . " up it El co:rrp a t 10 d of bor ic ox1dv. 'rhB
scavenger tower wag fed by an a ir l i f t from rOfJor ai r ho lding a pulp con-
si s t i ng of the solid s ob t1.i nod from t :--t€ f 1. t r (;.!. ti on of TO. I ovo r flow,
ba r r on li q or obt~ i. cd f r:>m t hu P l' \) i p i tu ti o t on - , a nd. mclco-u'!> wate r. Th()
pul p "JaG k l p t in pU Gpo .. ion -C'~ a mot or Bt l! r r. T.. G r a t a of fced in to tht;
se .von or t ow~ r we s ",c.j us tcd :0 Ii 00 t e e d..l 0: No . 1 tQ1.;1 r , solids '
fr in ::J. 1 f iltor boing ddod t o t he r 30l'voir r: ob t· i n.](l , tOgo thol' ..Ji th
on o 11 lor to g""'l v e vo lum' 0 ov crflO\"l fro t he c v onge:::- tc'..,rc~ r'll-
fici ont to naintv. in tho l'Ta. 1 r o!) ar vo ir at . Cl pr oxi mat ely const1..nt lov ell

Th o boric acid solu t.i n obt in d f ro m ' o. ') f i l t ar ,.ront to the p recipi ta-
t10n t a nk, \,~er it 'NaS h a ted t o d compo e ho c l cil!ID .:IDd magnes ium
bic.:lrbona t es p re '"" en t, t h an cf')o l ed , .n d t r en t ·lith suffi ciL;nt mi l k of li me
to give an end pH.o S o. t o 9.0. Th i .re sult. d i!1 'preci :9i t a tion of t:le
I
boric o~ ~ idG a 0 l.ci um bor t e I ":Ihic h u'~s f i 1 tared . driod, anel stored. The
lime u s ed \:m,s comme . :eia l-e,rad ...,hemieal, li c .

O ra-- tion
--

Th system ".,as op r ated on a ')4-~lour ba r is lor. three days to re l a te

t h e r at of f e ed of oli d , l i qui d , and ga n. T'l'le 0 j ecti ve \lia s to obt5.in
as ric a solution D.S p0 3f-d bl e I rom l~ o. 1 t o er \..ri th ffi ext ~a ctio n of
boric oxi de !1i g!1, en ou to 110 r th SCB.V or to 'lor t o , .e a.s ncp r1y
perf ct a. cl ean- up as p o s sib l After 3 da y s 0.1. ope r at ion, \"lth -oot ~l to' erR
0

f tmc t i oning satisf' ctoril~~, b <;>th t he feed hoppe r i n t o ;;0 . 1 t ower nod tho
precip i tat ion t ank Nere omp tied, t. e 1 vel of ulp foed i nto s cavengor
t o ',e_' and liq,uor f eod into No .1 to' er wore r1"od , and th~ p i l ot r was
,
start ed \'1i t h 200 pounds o ' co can tr t ~ g roUt: t o - 100 mo Tho :run \'Ja s
cont inuod f or 9 day s until tho 200 p 01 nd 0_ "t~ r i 1 had been cons umod,
and wa ended \.n th tho system i n t ho oo.me c ! di t i~ l s at 'tl begi r.ning ,
tha.t l s , oppe r and pr cin i t t i on t 1- e:nI ty , P 1p nd 1i Q.uo_ fe e d a t
origina l 1 v el, ~d both tower flu .

Control s ampl e!:) of the l i quor e r t ver,} 2 hO·,lT9 end of t~1f.'

t a i l ing s every 6 h urs. The l ate of r' ad jus t ed 0 the , ba sis of
theG8 o.na l y sas , but a f t er steadv 0 be !l I').cL l v e , ve ry 1i ttlc
adju t ment W 8 rAquire , the op r at i on b - i n~ l'r n~l" ~ut oma tic.

- l,6 -
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 R.I. 3 5~ 5

I At the conclus i on of th
sampled, and analy z d .
of t h produc t i S giv en i n t a .. l
Th d~ t
run , tailinF,s and product
0
4.
th rLm ~r e
~c re
'iv en in t a ble
dried , weighed,
3; anuly sis

TABLE 3. - a t~ on 20Q-no

T mperatur e of l eac s olut i o 0°-25° c.

Conc en t l'a t s f eed : 7 to 8 ms per minu t e or o.ppr oxima. t ~ly 1 pound per hour.
gl'"
Wat er feed : 100 to 120 !Ill . per i nu.te ,· or appr oxiJ:1El.t ol y 1.7 ga.l. p er hour.
, 3 0. 1 t ower li quor, :8 2°3 con ten t: 30 to 32 gram f.\ pe r lit e r.
.. Je . 2 te~J e" li qu r, B20~ con~ en t: 8 to 12 gre.."!l S pe r Ii t ar •
H ad "', ".ra i t: 200 pound ~'.
Reade , 203 cent t: 42 .46 pe rc nt, 84. 92 poun s .
Tail • '/ i ght: 100.5 )Jound s .
T 1 1 , B203 cont en t: 2. 33 per c e~t , . 34 po~d s .
B203, ext-a ct ed ~e i ht: 82 . 58 ~ounds .
Pcr conttLge ex'trnction: ~ x 100 = 97. 2 nc r ccnt.
84 . 92 .~

Tho se re sult , \-!hi l e i nd ica t i ng a high x t rac tion, p roba bly ould at!ll
b i mpr ovod i n prac ti co , :fo r cl.Ul'i ng th0 last 3 day~ 0 .( oper a ti on the ]203
cont en t oi t ~o t ails a vora 0 o , l y 1 . 08 ~erccn t, i~s t ead of 2.33 percent ,
gi v ng a n ex tra ~ti on of a l mo~ t 99 perc en t du i n . t he last par t of the
ope ... a t1on,

T.A.BL:E 4"

I :Recalculat ed to
ba is
B20 3 " . , ....... , ... , •• 53 . 31
S102 -' · ... , , , ..... , .. · 32
A120
3· ••. , .•.. , ..... • . 11 .15
Fe203' . · ' , .......... . . 11 .15
CaO •......... I ••••••• 3 . 07 41,23
MgO ••....••.•••. ,., •• . 60 .so
co ... , ........... ".. 1. 88 2.49
• SO, ..... , ... , . "..•... 1. 13 1 . 50
24 . 60
, F'"2 0 •.. , •• • • •••••••••.
~----------~-----------------

Of the i mpuri i es present , t he a r bon dioxide an d magnesi a may be r e-

moved Imo st co~ l etely , fo - t 'ley r e recl~itated n c l ci um and magnesium
ca r 0 te e when t he leac: liquor " being heatf}d n t h e pr c i p i t a t ion tank s
C!

to decompo e t h e bi carboUf'.t os presen t. The rat i os of ~i li ca , a.l umina , and

i ron to th e l i:oe PI' ~en t f're but Ii t tle 1i ' er than ..,'ltC r a t io . "or chemic 1
lime , an hen c' t!1e"'e s! Qu Id not l t !3rfa '9 , ff") any pur pose for which
chemi cal li m wou l ~ b~ u~ed , t h ~ o ~ ic oxide . The smal l amount of sulfat e,
hO\'1ev e r , \t/as an i mpuri. t y th.?t cou ld no t be remove b" epe t e ' . sh ng.

I
R. I. 3525
Conclusion

It is p os ibl to conc ontrate the calc ium bora te in· thi s colemanite
or e . by a 500 0 to 550 0 Cil 0 leine · f ollowed b;y acr eening . A ca rbonic acid
I
li".'1ch of t hi s conc entra t e gi ves an xtra ction of a l mos t 99 p~rcent of the
bo ric oxide, .,!li eh is r e c ove r ab le a s calci un: borat e 'by r ecipi t a ti on wi th
li ~ e . 'I'her e i no a c cu.nru.l _ti'on of trou·olesome impuri ti es in the closed
l each ci r cuit. A ada of cal ci~~ bora t e is obtained t hat has a number
of commex'cial u s e s, and i f wast e heat and "'laste CO 2 gas ~1ere used t the
pr ocess should be cO.IDPe ti t i ve wit h p re s ent sources of co mmercial borates.

It i s f el t· t hD. t 'th1 l a bor a t ory ha s ca rri e d thi s i nvesti gation to a .)

point whe re th e further "'ork- noc e sary to demonstra te the economic feasi-
bility sh ould be ca rri ed fo r ward by th indu s try ith er indep endent.ly or
i n co op er a tion \'11 th the Bureau.· .

7680 - 18 -
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