( 1 2 ) United S ta tes Pa tent

V a r a da r a j
US 006454936B1
( 1 0) Pa tent N 0. :
( 45) Da te o f Pa tent:
US 6, 454, 936 B1
S ep . 2 4, 2 002
( 54) REMOV AL OF ACIDS FROM OILS
( 7 5) Inv ento r : Ra mes h V a r a da r a j , Fl eming to n, N J
( Us )
( 7 3) As s ig nee: Exxo nMo bil Res ea r c h a nd
Eng ineer ing Co mp a ny , Anna nda l e, N J
( Us )
( * ) N o tic e: S u bj ec t to a ny dis c l a imer , the ter m o f this
p a tent is extended o r a dj u s ted u nder 35
U. S . C. 1 54( b) by 1 1 da y s .
( 2 1 ) Ap p l . N o . : 09/ 8 03, 57 3
( 2 2 ) Fil ed: Ma r . 9, 2 001
( 51 ) Int. Cl . 7 . . . . . . . . . . . . . . . . . . . . . . . . . C1 0G 45/ 1 4; C1 0G 45/ 56
( 52 ) US . Cl . . . . . . . . . . . . . . . . . . . . . . . . . 2 08 / 2 63; 2 08 / 2 99; 2 08 / 307
( 58 ) Fiel d o f S ea r c h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 08 / 2 63, 2 99,
2 08 / 307
( 56) Ref er enc es Cited
U. S . PATEN T DOCUMEN TS
2 , 42 4, 1 58 A 7 / 1 947 Fu qu a et a 1 . . . . . . . . . . . . . . . . . . . 1 96/ 41
3, 7 61 , 534 A * 9/ 1 97 3 S u n et a l . . . . . . . . . . . . . 2 08 / 2 30
4, 7 52 , 38 1 A 6/ 1 98 8 Fer g u s o n et a l . 2 08 / 2 63
5, 98 5, 1 37 A * 1 1 / 1 999 Ohs o l et a l . . . . . . . . . . 2 08 / 2 63
6, 096, 1 96 A 8 / 2 000 V a r a da r a j et a l . . . . . . . . . . . . 2 08 / 2 63
OTHER PUBLICATION S
“S o mo c hemic a l Tr ea tment o f Fo s s il Fu el s ” ; Ka Zem M.
S a deg hi, Jiu nn— Ren Lin; Teh Fu Y en; Ener g y S o u r c es , v o l .
1 6, p p . 439— 449, U. K. , Dep a r tment o f Civ il a nd Env ir o n
menta l Eng ineer ing , Univ er s ity o f S o u ther n Ca l if o r nia , Lo s
Ang el es , Ca l if o r nia .
An Up g r a ding Pr o c es s Thr o u g h Ca v ita tio n a nd S u r f a c ta nt;
Jiu nn— Ren Lin a nd Teh Fu Y en; Ener y & Fu el s 1 993, v o l . 7 ,
p p . 1 1 1 — 1 1 8 ; Dep a r tment o f Civ il a nd Env ir o nmenta l Eng i
neer ing , Univ er s ity o f S o u ther n Ca l if o r nia , Lo s Ang el es ,
Ca l if o r nia ; Rec eiv ed Ju n. 1 , 1 992 . Rev is ed Ma nu s c r ip t
Rec eiv ed Oc t. 6, 1 992 .
“Ul tr a s o u nd in S y nthes is ” ; Kenneth S . S u s l ic k ; Mo der n
S y nthetic Metho ds 1 98 6, v o l . 4; S c ho o l o f Chemic a l S c i
enc es Univ er s ity o f Il l ino is a t Ur ba na — Cha mp a ig n, 505 S .
Ma thews Av . , Ur ba na , Il l ino is 61 8 01 .
“Pr o c es s ing o f Res idu a l Oil Pr o du c ts by V is br a k ing in
Pr es enc e o f Additiv e in Fo r m o f Ar o ma tis ed Fr a c tio n o r
Ac eto ne, W ith Initia l Ca v ita tio n Tr ea tment o f S ta r ting Ma te
r ia l ” ; M. B. Ba s in, Gimbu ta s , A. S a nd V . Y u V a ino r a ;
Ma Zheik s k N a f ta Oil Re? ner y , ( Abs tr a c t Onl y ) .
“Us e o f the Ul tr a s o nic Ca v ita io n Ef f ec t o f Redu c e Oil
V is c o s ity a nd Inc r ea s e its Ra te o f Tr a ns p o r t” ; V . G. Andr eev ;
O. S . Br y u k ho v ets k ii; O. I. Po no ma r ev a a nd V . N . Ro di
o no v ; Pet. Abs tr . 658 , 1 09; IZv . V y s s h. Uc heb. Za v edenii,
Geo l . Ra Zv edk a ( 4) , ( Ju l . — Au g . 1 996) ; Us e o f theP Petr o
l eu m Abs tr a c ts ABS TR. N o . 658 , 1 09 V 37 , N 40, ( Oc t. 4,
1 997 ) , ( Abs tr a c t Onl y ) .
“Ca v ita tio n Metho d f o r Pr o c es s ing Petr o l eu m Re? ning
Res idu es ” ; Ak c ine Bendr o v e ’ Ma Zeik iu N a f ta ; Ba s in,
Mic ha il Bo r is o v ic ; ( Co p y r ig ht 1 997 by the Amer ic a n
Chemic a l S o c iety , CA 1 2 7 : 698 7 Q ) , ( Abs tr a c t Onl y ) .
“The Ef f ec ts o f Ul tr a s o nic Tr ea tment o n the V is c o s ity o f
Atha ba s c a Bitu men a nd Bitu men— S o l v ent Mixtu r es ” , A
Cha k ma a nd F. Ber r u ti; the Jo u r na l o f Ca na dia n Petr o l eu m
Tec hno l o g y , Ma y 1 993 ( v o l . 32 , N o . 5) ; p p . 48 — 51 .
“Ul tr a s o nic V is br ea k ing o f Atha ba s c a Bitu men” ; Amit
Cha k ma a nd Fr a nc o Ber r u ti; Petr o l eu m S o c iety o f CIM a nd
AOS TRA, Pa p er N o . CIM/ AOS TRA 91 — 9; Pr es ented a t the
CIM/ AOS TRA 1 991 Tec hnic a l Co nf er enc e in Ba nf f , Ap r .
2 1 — 2 4, 1 991 ; p p . 9— 1 to 9— 5.
“Ul tr a s o nic V is br ea k ing o f Atha ba s c a Bitu men” ; A. Cha k ma
a nd F. Ber r u ti, Dep a r tment o f Chemic a l a nd Petr o l eu m
Eng ineer ing , The Univ er s ity o f Ca l g a r y , Ca l g a r y , Al ber ta ,
Ca na da T2 N 1 N 4; p p . 1 01 — 1 04.
“Ul tr a s o nic V is br ea k ing o f Atha ba s c a Bitu men” ; A. Cha k ma
a nd F. Ber r u ti; Ener g y Pr o c es s ing / Ca na da ; S ep . — Oc t. , 1 991 ;
p p . 1 6— 1 9.
* c ited by exa miner
Pr ima r y Exa miner — W a l ter D. Gr if ? n
As s is ta nt Exa miner — Ta m M. N g u y en
( 7 4) Atto r ney , Ag ent, o r Fir m— Es tel l e C. Ba k u n
( 57 ) ABS TRACT
The ins ta nt inv entio n is dir ec ted to a p r o c es s f o r dec r ea s ing
the a mo u nt o f a c ids c o nta ined in o il s by f o r ming a W a ter
in- o il emu l s io n a nd u til iz ing s o l ids .
2 1 Cl a ims , N 0 Dr a wing s
US 6, 454, 936 B1
1
REMOV AL OF ACIDS FROM OILS
FIELD OF THE IN V EN TION
The ins ta nt inv entio n is dir ec ted to the r emo v a l o f a c ids ,
es p ec ia l l y o r g a nic a c ids s u c h a s na p hthenic a c ids f r o m o il s
inc l u ding c r u de o il s , c r u de o il bl ends a nd c r u de o il dis til l a tes
u s ing s o l ids .
BACKGROUN D OF THE IN V EN TION
Hig h To ta l Ac id N u mber ( TAN ) c r u des a r e dis c o u nted by
a bo u t $0. 50/ TAN / BBL. The do W ns tr ea m bu s ines s dr iv er to
dev el o p tec hno l o g ies f o r TAN r edu c tio n is the a bil ity to
r e? ne l o W c o s t c r u des . The u p s tr ea m dr iv er is to enha nc e the
ma r k et v a l u e o f hig h- TAN c r u des .
The c u r r ent a p p r o a c h to r e? ne a c idic c r u des is to bl end the
a c idic c r u des W ith no n a c idic c r u des s o tha t the TAN o f the
bl end is no hig her tha n a bo u t 0. 5. Mo s t ma j o r o il c o mp a nies
u s e this a p p r o a c h. The dr a W ba c k W ith this a p p r o a c h is tha t
it l imits the a mo u nt o f a c idic c r u de tha t c a n be p r o c es s ed.
Additio na l l y , it is k no W n in the a r t to tr ea t the c r u des W ith
ino r g a nic ba s es s u c h a s p o ta s s iu m a nd s o diu m hy dr o xide to
neu tr a l iZe the a c ids . This a p p r o a c h, ho W ev er , f o r ms emu l
s io ns W hic h a r e v er y dif ? c u l t to br ea k a nd, a dditio na l l y ,
u ndes ir a bl y l ea v es p o ta s s iu m o r s o diu m in the tr ea ted c r u de.
Fu r ther mo r e, s u c h p r io r a r t tec hniqu es a r e l imited by the
mo l ec u l a r W eig ht r a ng e o f the a c ids they a r e c a p a bl e o f
r emo v ing .
W ith the p r o j ec ted inc r ea s e o f a c idic c r u des in the ma r k et
( Cha d, V enez u el a , N o r th S ea ) neW tec hno l o g ies a r e needed
to f u r ther r e? ne hig her TAN c r u des a nd c r u de bl ends .
Ther ma l tr ea tment, s l u r r y hy dr o p r o c es s ing a nd c a l c iu m neu
tr a l iZa tio n a r e s o me o f the p r o mis ing a p p r o a c hes tha t ha v e
emer g ed. Ho W ev er , thes e tec hno l o g ies do no t extr a c t the
a c ids f r o m the c r u des . Ins tea d, they c o nv er t the a c ids to
p r o du c ts tha t r ema in in the c r u de.
US . Pa t. N o . 4, 7 52 , 38 1 is dir ec ted to a metho d f o r
neu tr a l iZing the o r g a nic a c idity in p etr o l eu m a nd p etr o l eu m
f r a c tio ns to p r o du c e a neu tr a l iZa tio n nu mber o f l es s tha n 1 . 0.
The metho d inv o l v es tr ea ting the p etr o l eu m f r a c tio n W ith a
mo no etha no l a mine to f o r m a n a mine s a l t f o l l o W ed by hea t
ing f o r a time a nd a t a temp er a tu r e s u f f ic ient to f o r m a n
a mide. S u c h a mines W il l no t a f f o r d the r es u l ts des ir ed in the
ins ta nt inv entio n s inc e they c o nv er t the na p hthenic a c ids ,
W her ea s the ins ta nt inv entio n extr a c ts a nd r emo v es them.
US . Pa t. N o . 2 , 42 4, 1 58 is dir ec ted to a metho d f o r
r emo v ing o r g a nic a c ids f r o m c r u de o il s . The p a tent u til iZes
a c o nta c t a g ent W hic h is a n o r g a nic l iqu id. S u ita bl e a mines
dis c l o s ed a r e mo no - , di- , a nd tr ietha no l a mine, a s W el l a s
methy l a mine, ethy l a mine, n- a nd is o p r o p y l a mine, n- bu ty l
a mine, s ec - bu ty l a mine, ter - bu ty l a mine, p r o p a no l a mine,
is o p r o p a no l a mine, bu ta no l a mine, s ec - bu ta no l , s ec - bu ta no l
a mine, a nd ter - bu ta no l a mine. The c o s t o f s u c h a mines f o r
r emo v a l o f na p hthenic a c ids a nd the need to r eg ener a te
them, ma k es s u c h a p r o c es s u nec o no mic a l . Henc e, a c o s t
ef f ec tiv e mea ns f o r r emo v a l o f na p hthenic a c ids is needed.
S UMMARY OF THE IN V EN TION
The ins ta nt inv entio n is dir ec ted to a p r o c es s f o r extr a c t
ing a c ids f r o m a s ta r ting o il c o mp r is ing the s tep s o f :
( a ) tr ea ting the s ta r ting o il c o nta ining a c ids W ith a n
a mo u nt o f s o l ids a nd W a ter u nder c o nditio ns a nd f o r a
time a nd a t a temp er a tu r e s u f ? c ient to f o r m a W a ter
in- o il emu l s io n o f s a id s ta r ting o il , W a ter a nd s o l ids
W her ein s a id s o l ids a r e s el ec ted f r o m s o l ids ha v ing a
to ta l a v er a g e s u r f a c e a r ea o f l es s tha n o r equ a l to 1 500
s qu a r e mic r o ns ;
1 5
2 0
2 5
30
35
40
45
50
55
60
65
2
( b) s ep a r a ting s a id emu l s io n o f s tep ( a ) into a p l u r a l ity o f
l a y er s W her ein o ne o f s u c h l a y er s c o nta ins a tr ea ted o il
ha v ing dec r ea s ed a mo u nts o f o r g a nic a c ids ;
( c ) r ec o v er ing s a id l a y er o f s tep ( b) c o nta ining s a id tr ea ted
o il ha v ing a dec r ea s ed a mo u nt o f o r g a nic a c id a nd
l a y er s c o nta ining W a ter a nd s o l ids .
DETAILED DES CRIPTION OF THE
IN V EN TION
In the ins ta nt inv entio n s o l ids a r e a dded to s ta r ting o il ( the
o il f r o m W hic h a c ids a r e to be r emo v ed) a l o ng W ith W a ter to
f o r m a n emu l s io n W hic h is then br o k en, s ep a r a ted into l a y er s
a nd the o il ha v ing dec r ea s ed a mo u nts o f a c id r ec o v er ed.
Bene? c ia l l y , the p r o c es s c a n be p r a c tic ed u s ing exis ting
o il / W a ter s ep a r a tio n equ ip ment W ith mino r mo di? c a tio ns .
The s o l ids ma y be s el ec ted f r o m s o l ids ha v ing a n a v er a g e
s u r f a c e a r ea o f l es s tha n o r equ a l to 1 500 s qu a r e mic r o ns ,
p r ef er a bl y f r o m a bo u t 2 5 to a bo u t 1 500 s qu a r e mic r o ns , a nd
mo s t p r ef er a bl y a bo u t 50 to a bo u t 1 500 s qu a r e mic r o ns , a nd
mo r e p r ef er a bl y a bo u t 1 00 to a bo u t 1 500 s qu a r e mic r o ns .
S u ita bl y , the s o l ids ma y be s el ec ted f r o m s il ic a , a l u mina ,
c o k e, mo ntmo r il l o nite c l a y s s u c h a s bento nite, k a o l inite, a nd
mixtu r es ther eo f . Al tho u g h o ther f o r ms a r e l ik eW is e u s ea bl e,
W hen c l a y s a r e s el ec ted, es p ec ia l l y bento nite c l a y , the c l a y
W il l p r ef er a bl y be in the g el f o r m. In the g el f o r m the c l a y
s heets a r e div ided o r exf o l ia ted. The p r o c edu r e to p r ep a r e
exf o l ia ted o r div ided g el is k no W in the a r t. The ma in
a dv a nta g e o f u s ing the exf o l ia ted c l a y is tha t the c l a y s o l ids
a r e in the f o r m o f s heets tha t a r e <tha n 1 0 nm thic k a nd c a n
be br o k en to 50 to 2 00 nm s iZe p l a tes . The s o l ids u til iZed
her ein a r e hy dr o p hil ic , hy dr o p ho bic o r a mp hip hil ic . The
s o l ids a r e p r ef er r a bl y a mp hip hil ic W hic h mea ns tha t they
ha v e a hy dr o p hil ic / hy dr o p ho bic c ha r a c ter . One s k il l ed in the
a r t r ea dil y c a n identif y s u c h s o l ids .
The inv entio n is p a r tic u l a r l y a p p l ic a bl e to c r u de o il s ,
c r u de o il bl ends , a nd c r u de o il dis til l a tes a nd mixtu r es
ther eo f . S o me c r u de o il s c o nta in o r g a nic a c ids tha t g ener a l l y
f a l l into the c a teg o r y o f na p hthenic a c ids a nd o ther o r g a nic
a c ids . N a p hthenic a c id is a g ener ic ter m u s ed to identif y a
mixtu r e o f o r g a nic a c ids p r es ent in a p etr o l eu m s to c k .
N a p hthenic a c ids ma y be p r es ent either a l o ne o r in c o mbi
na tio n W ith o ther o r g a nic a c ids , s u c h a s s u l f o nic a c ids a nd
p heno l s . Thu s , the ins ta nt inv entio n is p a r tic u l a r l y s u ita bl e
f o r extr a c ting na p hthenic a c ids .
In the ins ta nt inv entio n, o r g a nic a c ids , inc l u ding na p h
thenic a c ids W hic h a r e r emo v ed f r o m the s ta r ting o il o r
bl ends a r e p r ef er a bl y tho s e ha v ing mo l ec u l a r W eig hts r a ng
ing f r o m a bo u t 1 50 to a bo u t 8 00, mo r e p r ef er a bl y , f r o m
a bo u t 2 00 to a bo u t 7 50. The ins ta nt inv entio n p r ef er a bl y
s u bs ta ntia l l y extr a c ts o r s u bs ta ntia l l y dec r ea s es the a mo u nt
o f na p hthenic a c ids p r es ent in the s ta r ting o il W hen the o il is
a c r u de o il o r c o mbina tio n ther eo f . By s u bs ta ntia l l y is mea nt
a l l o f the a c ids exc ep t f o r tr a c e a mo u nts . Ho W ev er , it is no t
nec es s a r y f o r s u bs ta ntia l l y a l l o f the a c ids to be r emo v ed
s inc e the v a l u e o f the tr ea ted c r u de is inc r ea s ed if ev en a
p o r tio n o f the na p hthenic a c ids a r e r emo v ed. Ap p l ic a nts
ha v e f o u nd tha t the a mo u nt o f na p hthenic a c ids c a n be
r edu c ed by a t l ea s t a bo u t 30%, p r ef er a bl y a t l ea s t a bo u t 60%
a nd, mo r e p r ef er a bl y , a t l ea s t a bo u t 8 6%.
S ta r ting o il s ( inc l u ding s ta r ting c r u des ) a s u s ed her ein
inc l u de a ny o il c o nta ining a c ids , a nd es p ec ia l l y c r u de o il s ,
c r u de bl ends , dis til l a tes a nd mixtu r es ther eo f . Al l tha t is
nec es s a r y is tha t the s ta r ting o il c o nta in a c ids , s u c h a s
o r g a nic a c ids a nd p r ef er a bl y na p hthenic a c ids . Pr ef er a bl y , if
the s ta r ting o il is a c r u de o il , the s ta r ting c r u de W il l be a
W ho l e c r u de, bu t c a n a l s o be a c idic f r a c tio ns ( o r dis til l a tes )
US 6, 454, 936 B1
3
o f a W ho l e c r u de s u c h a s a v a c u u m g a s o il . The s ta r ting o il s
a r e tr ea ted W ith a n a mo u nt o f s o l id c a p a bl e o f a ds o r bing the
a c ids p r es ent in the s ta r ting o il . This ty p ic a l l y W il l be f r o m
a bo u t 0. 1 to a bo u t 5 W t % ba s ed o n the a mo u nt o f o il being
tr ea ted a nd the a mo u nt o f a c ids p r es ent. The ins ta nt inv en
tio n is c a p a bl e o f r emo v ing na p hthenic a c ids r a ng ing in
mo l ec u l a r W eig ht f r o m a bo u t 1 50 to a bo u t 8 00, p r ef er a bl y
a bo u t 2 50 to a bo u t 7 50. The W eig ht r a ng es f o r the na p h
thenic a c ids r emo v ed ma y v a r y u p W a r d o r do W nW a r d o f the
nu mber s her ein p r es ented, s inc e the r a ng es a r e dep endent
u p o n the s ens itiv ity l ev el o f the a na l y tic a l mea ns u s ed to
deter mine the mo l ec u l a r W eig hts o f the na p hthenic a c ids
r emo v ed.
The s o l ids c a n be a dded a l o ne o r in c o mbina tio n W ith
W a ter . If a dded in c o mbina tio n, a s o l u tio n o f the s o l id a nd
W a ter ma y be p r ep a r ed. Abo u t 5 to 30 W t % W a ter is a dded
ba s ed u p o n the a mo u nt o f c r u de o il . Pr ef er r a bl y 5 to 1 0 W t
%. W hether the s o l ids a r e a dded in c o mbina tio n W ith the
W a ter o r p r io r to the W a ter , the c r u de is tr ea ted f o r a time a nd
a t a temp er a tu r e a t W hic h a W a ter - in- o il emu l s io n o f W a ter ,
o il , s o l ids a nd o r g a nic a c ids W il l f o r m. Co nta c ting times
dep end u p o n the na tu r e o f the s ta r ting c r u de to be tr ea ted, its
a c id c o ntent, a nd the a mo u nt o f s o l id a dded. The temp er a
tu r e o f r ea c tio n is a ny temp er a tu r e tha t W il l a f f ec t f o r ma tio n
o f the W a ter - in- o il emu l s io n. Ty p ic a l l y , the p r o c es s is c o n
du c ted a t temp er a tu r es o f a bo u t 2 0 to a bo u t 2 2 0° C. ,
p r ef er a bl y , a bo u t 2 5 to a bo u t 1 30° C. , mo r e p r ef er a bl y , 2 5 to
8 0° C. The c o nta c t times W il l r a ng e f r o m a bo u t 1 minu te to
1 ho u r a nd, p r ef er a bl y , f r o m a bo u t 3 to a bo u t 30 minu tes .
Pr es s u r es W il l r a ng e f r o m a tmo s p her ic , p r ef er a bl y f r o m
a bo u t 60 p s i ( 41 3. 7 k Pa ) a nd, mo r e p r ef er a bl y , f r o m a bo u t
60 to a bo u t 1 000 p s i ( 41 3. 7 k Pa to a bo u t 68 95 k Pa ) . Fo r
hea v ier c r u des , the hig her temp er a tu r es a nd p r es s u r es a r e
des ir a bl e. The c r u de is then mixed W ith W a ter , if s tep W is e
a dditio n is p er f o r med a t a temp er a tu r e a nd f o r a time
s u f f ic ient to f o r m a n emu l s io n. The times a nd temp er a tu r es
r ema in the s a me f o r s imu l ta neo u s a dditio n a nd s tep W is e
a dditio n o f the W a ter . If the a dditio n is do ne s imu l ta neo u s l y ,
the mixing is c o ndu c ted s imu l ta neo u s l y W ith the a dditio n a t
the temp er a tu r es a nd f o r the times des c r ibed a bo v e. It is no t
nec es s a r y f o r the s imu l ta neo u s a dditio n to mix f o r a n
a dditio na l p er io d. Thu s , tr ea tment o f the s ta r ting c r u de
inc l u des bo th c o nta c ting a nd a g ita tio n to f o r m a n emu l s io n,
f o r exa mp l e, mixing . Hea v ier c r u des , s u c h a s tho s e W ith API
indic es o f 2 0 o r l o W er a nd v is c o s ities g r ea ter tha n 2 00 c P a t
2 5° C. , p r ef er a bl y , W il l be tr ea ted a t temp er a tu r es a bo v e 60°
C.
Onc e the W a ter in o il emu l s io n ha s been f o r med, it is
s ep a r a ted, p r ef er a bl y , it is s u bj ec ted to s o nic a tio n a nd then
s ep a r a ted into a p l u r a l ity o f l a y er s . The s ep a r a tio n c a n be
a c hiev ed by mea ns k no W n to tho s e s k il l ed in the a r t. Fo r
exa mp l e, c entr if u g a tio n, g r a v ity s ettl ing , s o nic a tio n,
hy dr o c y c l o nes , mic r o W a v e, el ec tr o s ta tic s ep a r a tio n a nd
c o mbina tio ns ther eo f .
It ma y be nec es s a r y to s o nic a te the emu l s io n p r io r to
s ep a r a ting into o il a nd W a ter l a y er s . This W il l be r ea dil y
ev ident to the s k il l ed a r tis a n s inc e the o ther c o mmo nl y
u til iZed tec hniqu es f o r s ep a r a tio n no ted a bo v e W il l f a il to
s ep a r a te the emu l s io n. Thu s , s o nic a tio n ma y be nec es s a r y to
br ea k the emu l s io n p r io r to s ep a r a tio n into l a y er s . S o nic a
tio n W il l be c o ndu c ted a t temp er a tu r es r a ng ing f r o m a bo u t
2 0 to a bo u t 2 50° C. a t a mbient p r es s u r es u p to a bo u t 2 00
p s ig ( 1 48 0 k Pa ) . Co ntinu ed s o nic a tio n o r a n a l ter na tiv e
s ep a r a tio n mea ns c a n then be emp l o y ed to ef f ec t the s ep a
r a tio n. A p l u r a l ity o f l a y er s r es u l t f r o m the s ep a r a tio n.
Ty p ic a l l y , a t l ea s t thr ee l a y er s W il l be p r o du c ed. The u p p er
mo s t l a y er c o nta ins the s ta r ting o il f r o m W hic h the a c ids
1 0
1 5
2 0
2 5
30
35
40
45
50
55
60
65
4
ha v e been r emo v ed. The s o l ids ha v ing a ds o r bed ther eo n
hig h a nd mediu m W eig ht a c ids W il l f o r m the inter media te
l a y er , W hil e the bo tto m l a y er is a n a qu eo u s l a y er c o nta ining
the a dded W a ter a nd o ther c o mp o nents c o nta ined in the
c r u de tha t ma y ha v e dis s o l v ed in the W a ter . The u p p er mo s t
l a y er c o nta ining tr ea ted o il is ea s il y r ec o v er a bl e by the
s k il l ed a r tis a n. Thu s , u nl ik e the tr ea tments u s ed in the p a s t
W her eby the a c ids a r e c o nv er ted into p r o du c ts W hic h r ema in
in the o il , the ins ta nt p r o c es s r emo v es the a c ids f r o m the o il .
Additio na l l y , tho u g h no t r equ ir ed, demu l s i? c a tio n a g ents
ma y be u s ed to enha nc e the r a te o f demu l s i? c a tio n a nd
c o - s o l v ents , s u c h a s a l c o ho l s , ma y be u s ed a l o ng W ith the
W a ter .
Us e o f demu l s i? er s in the inv entio n is o p tio na l . If s u c h
demu l s i? er s a r e u til iZed, the demu l s i? er s W il l be s el ec ted
f r o m a ny k no W n demu l s i? er s a nd W hen a s o nic a tio n s tep is
u s ed f o r s ep a r a tio n the demu l s i? er c ho ic e is r es tr ic ted to
tho s e tha t W il l no t deg r a de du r ing s o nic a tio n. S u c h demu l
s i? er s c a n be r ea dil y s el ec ted. Ty p ic a l l y , the demu l s i? er s
u til iZed W hen s o nic a tio n is emp l o y ed W il l ha v e a mo l ec u l a r
W eig ht o f a bo u t 500 to a bo u t 5000, p r ef er a bl y a bo u t 500 to
a bo u t 2 000 a nd a hy dr o p hil ic l ip o p hil ic ba l a nc e o f a bo v e 9,
p r ef er a bl y a bo u t 9 to a bo u t 30 a nd mo s t p r ef er a bl y a bo u t 9
to a bo u t 1 5. Demu l s i? er s W hic h W il l no t deg r a de du r ing
s o nic a tio n W il l no t c o nta in f u nc tio na l g r o u p s s u c h a s es ter s
o r a mides . Us ea bl e demu l s i? er s W il l inc l u de, bu t a r e no t
l imited to tho s e W hic h c o nta in f u nc tio na l g r o u p s s u c h a s
ether s , a mines , etho xy l a ted a l c o ho l s , s u l f o na tes a nd mix
tu r es ther eo f . A p a r tic u l a r l y p r ef er r ed demu l s i? er is a p he
no l f o r ma l dehy de etho xy l a ted p r o p o xy l a ted r es in. W hen no
s o nic a tio n is a p p l ied, a ny demu l s i? er k no W n to the s k il l ed
a r tis a n c a n be emp l o y ed to demu l s if y the emu l s io n.
The demu l s i? er W il l be a dded to the emu l s io n a f ter s o l ids
a dditio n a nd p r io r to the s ep a r a tio n s tep . The a mo u nt o f
demu l s i? er to be a dded W il l r a ng e f r o m a bo u t 0. 1 to a bo u t
5. 0 W t % ba s ed o n the a mo u nt o f the emu l s io n. Additio na l l y ,
a del iv er y s o l v ent ma y be emp l o y ed. S u c h s o l v ents ma y
inc l u de c r u de o il dis til l a tes bo il ing in the r a ng e o f a bo u t 7 0°
C. to a bo u t 450° C. , a l c o ho l s , ether s a nd mixtu r es ther eo f .
Thu s , the del iv er y s o l v ents ma y be s el ec ted f r o m the g r o u p
c o ns is ting o f the a bo v e.
The del iv er y s o l v ent W il l be p r es ent in a n a mo u nt o f f r o m
a bo u t 35 to a bo u t 7 5 W t % in the demu l s i? er . Thu s , W hen
u til iZed, the del iv er y s o l v ent W il l be inc l u ded in the 0. 1 to
5 . 0 W t % demu l s i? er a dded to the emu l s io n.
A p a r tic u l a r y p r ef er r ed demu l s i? er is a p heno l f o r ma l de
hy de etho xy l a ted a l c o ho l ha v ing the s tr u c tu r e:
W her ein R is s el ec ted f o r m the g r o u p c o ns is ting o f a l k a nes
o r a l k enes f r o m 8 to 2 0 c a r bo ns , E is CH2 — CH2 a nd P is
— CH2 — CH— CH3, n r a ng es f r o m 1 to 5, m
H H H
( ‘ LOB ( LOB ( PO) . . .
( B0) “ ( 1 : 50) “ ( E0) ,
0 O 0
CH2 CH2
R R X R
r a ng es f r o m 0 to 5 a nd x r a ng es f r o m 3 to 9.
US 6, 454, 936 B1
5
In the ins ta nt inv entio n, it ma y be nec es s a r y to a p p l y s o nic
ener g y to br ea k the inter f a c ia l ? l m p r es ent in the W a ter - in- o il
emu l s io n f o r med.
If s o nic a tio n is r equ ir ed, it is ty p ic a l l y a c c o mp l is hed a t
ener g ies o f a bo u t 2 5 to a bo u t 500 W a tts / c m2 . The v el o c ity o f
s o u nd in l iqu ids is ty p ic a l l y a bo u t 1 500 meter s / s ec . Ul tr a
s o u nd s p a ns the f r equ enc y o f a bo u t 1 5 k HZ to 1 0 MHZ W ith
a s s o c ia ted W a v el eng ths o f a bo u t 1 0 to 0. 02 c m. The inv en
tio n ma y be p r a c tic ed a t f r equ enc ies o f a bo u t 1 5 k HZ to
a bo u t 2 0 MHZ. The o u tp u t ener g y a t a g iv en f r equ enc y is
exp r es s ed a s s o nic a tio n ener g y in u nits o f W a tts / c m2 . The
s o nic a tio n p r o v ided f o r in the ins ta nt inv entio n is ty p ic a l l y
a c c o mp l is hed a t ener g ies o f a bo u t 2 5 to a bo u t 500 W a tts /
c m2 .
Fo l l o W ing the s o nic a tio n, the s o nic a ted emu l s io n is s ep a
r a ted by metho ds s u c h a s c entr if u g a tio n, hy dr o c y c l o nes ,
mic r o wa v e, s o nic a tio n, g r a v ity s ettl ing , el ec tr o s ta tic ? el d,
c o mbina tio ns ther eo f , o r by a ny o ther metho ds k no W n to the
s k il l ed a r tis a n f o r p ha s e s ep a r a tio n. The o il ma y then be
r ec o v er ed a s a s ep a r a te p ha s e.
To deter mine the a mo u nt o f s o nic ener g y nec es s a r y to
br ea k the inter f a c ia l ? l m o f the emu l s io n, a s er ies o f s a mp l es
o f the W a ter - in- o il emu l s io n a r e tr ea ted by a p p l y ing s o nic
ener g y . At l ea s t thr ee s a mp l es W il l f o r m the s er ies . Ty p ic a l l y ,
a t l ea s t 3 to 2 0 s a mp l es , a nd mo r e p r ef er a bl y a t l ea s t 3 to 1 0
s a mp l es , a nd mo r e p r ef er a bl y 3 to 5 s a mp l es W il l be u til iZed.
The s o nic ener g y is a p p l ied to ea c h s a mp l e, W ith ea c h
p r o c eeding s a mp l e being s o nic a ted a t a n ener g y a t l ea s t
a bo u t 2 5 to a bo u t 50 W a tts / c m2 hig her tha n the p r ec eeding
s a mp l e. Onc e s o nic a tio n is c o mp l ete, the s a mp l es a r e s ep a
r a ted into a W a ter p ha s e a nd a n o il p ha s e o r l a y er a nd the
p er c ent W a ter demu l s i? ed o r s ep a r a ted o u t is mea s u r ed. A
ma ximu m a mo u nt o f W a ter demu l s i? ed c a n then be identi
? ed a nd the ener g y o f s o nic a tio n c o r r es p o nding to the
a mo u nt a p p l ied to p r o du c e the hig hes t qu a ntity o f W a ter
demu l s i? ed is equ iv a l ent to the s tr eng th o f the inter f a c ia l
? l m o f the emu l s io n. The a mo u nt o f ener g y to be a p p l ied to
the ? r s t o f the s er ies o f s a mp l es is a bo u t 2 5 to a bo u t 50
W a tts / c m2 .
One s k il l ed in the a r t W il l r ea dil y r ec o g niZe tha t the s o nic
ener g y to be a p p l ied to br ea k the inter f a c ia l ? l m o f the
emu l s io n, if nec es s a r y , c a n be l o W er ed by u s e o f a demu l
s i? er .
The p r o c es s c a n be c o ndu c ted u til iZing exis ting des a l ter
u nits . The p r o c es s is a p p l ic a bl e to bo th p r o du c tio n a nd
r e? ning o p er a tio ns . In the r e? ner y , the a c idic o il s tr ea m is
tr ea ted W ith the r equ ir ed a mo u nt o f s o l ids by a dding the
s o l ids to the c r u de o il a nd mixing W ith a s ta tic mixer a t l o W
s hea r . Al ter na tiv el y , the s o l ids c a n be a dded ? r s t, mixed a nd
f o l l o W ed by W a ter a dditio n a nd mixing . The tr ea ted s ta r ting
o il W hic h is a c r u de o il , c r u de o il bl end o r c r u de dis til l a te is
then s u bj ec ted to s o nic a tio n, if nec es s a r y , f o l l o W ed by
demu l s i? c a tio n o r s ep a r a tio n in a des a l ting u nit W hic h
a p p l ies a n el ec tr o s ta tic ? el d o r o ther s ep a r a tio n mea ns . The
o il W ith r edu c ed TAN is dr a W n o f f a t the to p a nd s u bj ec ted
to f u r ther r e? ning if des ir ed. The middl e a nd l o W er a qu eo u s
p ha s es a r e dr a W n o f f a nd dis c a r ded. The middl e l a y er
c o nta ining the s o l ids a nd extr a c ted na p hthenic a c ids c a n be
tr ea ted by metho ds k no W n to tho s e in the a r t, to p r o du c e a
no n- c o r r o s iv e p r o du c t, o r dis c a r ded a s W el l .
The f o l l o W ing exa mp l es a r e mea nt to be il l l u s tr a tiv e a nd
no t l imiting in a ny W a y .
5
1 0
1 5
2 0
2 5
30
35
40
45
50
55
60
65
6
EX AMPLES 1 — 7
The g ener a l p r o c edu r e to p r ep a r e a W a ter - in- c r u de o il
emu l s io n inv o l v ed a dding s o l ids ( 0. 1 5 W t % ba s ed o n W eig ht
o f o il ) to the o il f o l l o W ed by a dditio n o f W a ter o r br ine a nd
mixing . A S il v er s o n mixer s u p p l ied by S il v er s o n Ma c hines ,
Inc . Ea s t Lo ng mea do W , Ma s s . W a s u s ed. Mixing W a s c o n
du c ted a t 2 5° C. a nd a t 400 to 600 r p m f o r a time r equ ir ed
to dis p er s e a l l the W a ter into the o il . W a ter W a s a dded to the
c r u de o il in a l iqu o ts s p r ea d o v er 5 a dditio ns . W hen demu l
s i? er W a s u s ed it W a s a dded to the emu l s io n a t a tr ea t r a te o f
0. 4 to 0. 5 W t % demu l s i? er f o r mu l a tio n ba s ed o n the W eig ht
o f emu l s io n a nd mixed W ith a S il v er s o n mixer a t 400 to 600
r p m f o r 1 0 to 1 5 minu tes . Ap heno l f o r ma l dehy de etho xy
l a ted a l c o ho l demu l s i? er f o r mu l a tio n s o l d by BAS E Co r p o
r a tio n a s Pl u r a dy ne DB7 946 W a s u s ed.
Centr if u g a tio n W a s c o ndu c ted a t 2 5° C. u s ing a Bec k ma n
L8 - 8 0 Ul tr a c entr if u g e a t 1 0, 000 r p m ( 7 7 8 0 g ) f o r 30 minu tes
to ef f ec t s ep a r a tio n o f the W a ter a nd o il p ha s es . S o nic a tio n
W a s c o ndu c ted u s ing a S o ni? er Mo del 350. The p u l s e mo de
o p er a ting a t a n o u tp u t c o ntr o l s etting o f 4 W a s u s ed a nd
s o nic a tio n c o ndu c ted f o r 2 minu tes . At the c o ntr o l s etting o f
4 the o u tp u t ener g y is a bo u t 1 50 W a tts / c m2 . The f r equ enc y
o f the s o nic W a v es W a s 2 0 k HZ. El ec tr o s ta tic demu l s i? c a tio n
W a s c o ndu c ted u s ing a mo del EDPT- 1 2 8 TM el ec tr o s ta tic
dehy dr a to r a nd p r ec ip ita tio n tes ter a v a il a bl e f r o m IN TER
AV , Inc . , S a n Anto nio , Tex. Demu l s i? c a tio n W a s c o ndu c ted
a t a n 8 30 v o l t/ inc h p o tentia l f o r 30 to 1 8 0 minu tes a t
temp er a tu r es o f 60 a nd 8 5° C.
TW o c r u de o il s , Ko me a nd Tu l a r e f r o m W es t Af r ic a a nd
US A r es p ec tiv el y W er e u s ed. Hy dr o p ho bic s il ic a s o l d u nder
the tr a de na me Aer o s il R 97 2 by DeGu s s a Co r p o r a tio n a nd
hy dr o p ho bic bento nite c l a y ( p r ep a r ed in the l a bo r a to r y by
exp o s ing div ided/ del a mina ted c l a y to c r u de o il a nd a ir
o xida tio n) W er e u s ed a s the s il ic a a nd c l a y s o l ids .
In a ty p ic a l exp er iment 30 to 40 g r a ms o f emu l s io n W er e
W eig hed into g r a du a ted c entr if u g e tu bes o r el ec tr o s ta tic c el l s
tu bes a nd tr ea ted a s indic ted in Ta bl e- 1 . Af ter s ep a r a tio n
thr ee l a y er s W er e o bs er v ed. The na p hthenic a c a id c o ntent o f
the u p p er o il l a y er W a s deter mined by Fo u r ier Tr a ns f o r m
Inf r a Red ( FTIR) metho d k no W n to o ne s k il l ed in the a r t o f
c r u de o il a na l y s es .
Res u l ts in Ta bl e- 1 c o mp a r e p er f o r ma nc e o f s o l ids a ddi
tio n to no s o l ids a dditio n a nd to demu l s i? er a dditio n a r e
p r o v ided.
EX AMPLE 8
A 40/ 30/ 30: Is o p a r - M/ S o l v ent 600 N / Ar o ma tic 1 50 W a s
u s ed a s a mo del o il ( Oil M) , W ith 5- beta c ho l a nic a c id a s a
mo del na p hthenic a c id. A 1 % s o l u tio n o f a c id W a s ma de W ith
the Mo del M o il . To 7 g o f this o il W a s a dded 3 g o f W a ter
a nd a n W a ter - in- o il emu l s io n p r ep a r ed. To the emu l s io n W a s
a dded 0. 1 5 W t % div ided bento nite g el a nd mixed. The
mixtu r e W a s then c entr if u g ed to s ep a r a te the o il a nd W a ter
p ha s es W ith the a p p r ea r a nc e o f a n inter media te l a y er . Inf r a
r ed a na l y s es W a s c o ndu c ted o n the u p p er o il l a y er .
US 6, 454, 936 B1
TABLE 1
S o l ids Oil / W a ter S o nic a tio n A
Exa mp l e Cr u de Oil W a ter Added Ra tio Demu l s i? er 1 50 W a tts / c m 2 S ep a r a tio n Mea ns % N a p Ac id Redu c tio n
1 Ko me Ko me Br ine N o ne 40/ 60 N o ne N o ne Centr if u g a tio n 0
2 Ko me Ko me Br ine Cl a y 40/ 60 N o ne 2 minu tes Centr if u g a tio n 8 6
3 Ko me Ko me Br ine N o ne 8 0/ 2 0 0. 5 W t % N o ne El ec tr o s ta tic 32
4 Ko me Ko me Br ine N o ne 8 0/ 2 0 0. 5 W t % 2 minu tes El ec tr o s ta tic 35
5 Ko me Ko me Br ine Cl a y 8 0/ 2 0 0. 5 W t % 2 minu tes El ec tr o s ta tic 8 6
6 Tu l a r e Tu l a r e Br ine N o ne 7 0/ 30 N o ne N o ne Centr if u g a tio n 0
7 Tu l a r e Tu l a r e Br ine S il ic a 7 0/ 30 N o ne 2 minu tes Centr if u g a tio n 47
8 Oil M W a ter Cl a y 7 0/ 30 N o ne N o ne Centr if u g a tio n 8 5
W ha t is c l a imed is : 1 5 g r o u p s s el ec ted f r o m the g r o u p c o ns is ting o f ether s , a mines ,
1 . Ap r o c es s f o r extr a c ting o r g a nic a c ids f r o m a s ta r ting o il
c o mp r is ing the s tep s o f :
( a ) tr ea ting the s ta r ting o il c o nta ining o r g a nic a c ids W ith
a n a mo u nt o f s o l ids a nd W a ter u nder c o nditio ns a nd f o r
a time a nd a t a temp er a tu r e s u f f ic ient to f o r m a W a ter
in- o il emu l s io n o f s a id s ta r ting o il , W a ter a nd s o l ids
W her ein s a id s o l ids a r e s el ec ted f r o m s o l ids ha v ing a
to ta l a v er a g e s u r f a c e a r ea o f l es s tha n o r equ a l to 1 500
s qu a r e mic r o ns ;
( b) s ep a r a ting s a id emu l s io n o f s tep ( a ) into a p l u r a l ity o f
l a y er s W her ein o ne o f s u c h l a y er s c o nta ins a tr ea ted o il
ha v ing dec r ea s ed a mo u nts o f o r g a nic a c ids ;
( c ) r ec o v er ing s a id l a y er o f s tep ( b) c o nta ining s a id tr ea ted
o il ha v ing a dec r ea s ed a mo u nt o f o r g a nic a c id a nd
l a y er s c o nta ining W a ter a nd s o l ids W her ein s a id s o l ids
a r e s el ec ted f r o m s il ic a , a l u mina , c o k e, mo ntmo r il l o
nite c l a y s , a nd mixtu r es ther eo f .
2 . The p r o c es s o f c l a im 1 W her ein s a id W a ter is a dded
s imu l ta neo u s l y W ith o r f o l l o wing s a id s o l ids .
3. The p r o c es s o f c l a im 1 W her ein the a mo u nt o f W a ter
a dded is a bo u t 5 to a bo u t 1 0% ba s ed u p o n the W eig ht o f the
s ta r ting c r u de o il .
4. The p r o c es s o f c l a im 1 W her ein s a id a mo u nt o f s o l ids
is a bo u t 0. 1 to 5 W t % ba s ed o n the W eig ht o f o il .
5. The p r o c es s o f c l a im 1 W her ein s a id s tep s ( a ) a nd ( b)
a r e c o ndu c ted a t temp er a tu r es o f a bo u t 2 0 to a bo u t 2 2 0° C.
6. The p r o c es s o f c l a im 1 W her ein s a id s tep s ( a ) a nd ( b)
a r e c o ndu c ted f o r times o f a bo u t o ne minu te to a bo u t o ne
ho u r .
7 . The p r o c es s o f c l a im 5 W her ein W hen s a id s ta r ting o il
is a c r u de o il a nd s a id c r u de o il ha s a n API index o f a bo u t
2 0 o r l o W er , s a id temp er a tu r e is a bo v e a bo u t 60° C.
8 . The p r o c es s o f c l a im 1 W her ein s a id s ep a r a tio n s tep ( b)
is a c hiev ed u s ing g r a v ity s ettl ing , el ec tr o s ta tic ? el d
s ep a r a tio n, c entr if u g a tio n o r a c o mbina tio n ther eo f .
9. The p r o c es s o f c l a im 1 W her ein c o - s o l v ents a r e a dded
W ith s a id W a ter .
1 0. The p r o c es s o f c l a im 1 W her ein demu l s i? er s a r e a dded
to s a id s ep a r a tio n s tep .
1 1 . The p r o c es s o f c l a im 9 W her ein s a id c o - s o l v ent is a n
a l c o ho l .
1 2 . The p r o c es s o f c l a im 1 0 W her ein s a id demu l s i? er is
s el ec ted f r o m a demu l s i? er ha v ing a mo l ec u l a r W eig ht o f
a bo u t 500 to a bo u t 5000 a nd W hic h c o nta ins f u nc tio na l
2 0
2 5
30
35
40
45
50
55
etho xy l a ted a l c o ho l s , s u l f o na tes , a nd mixtu r es ther eo f .
1 3. The p r o c es s o f c l a im 1 0 W her ein s a id demu l s i? er is
a dded in a n a mo u nt o f a bo u t 0. 1 to a bo u t 5. 0 W t %.
1 4. The p r o c es s o f c l a im 1 3 W her ein a bo u t 35 to a bo u t 7 5
W t % o f a del iv er y s o l v ent is a dded to s a id demu l s i? er .
1 5. The p r o c es s o f c l a im 1 W her ein s a id p r o c es s is
c o ndu c ted in a r e? ner y a nd s a id s ep a r a tio n is c o ndu c ted in
a des a l ting u nit to p r o du c e a p ha s e c o nta ining a tr ea ted c r u de
ha v ing o r g a nic a c ids r emo v ed ther ef r o m, a nd p ha s e c o n
ta ining W a ter .
1 6. The p r o c es s o f c l a im 1 W her ein s a id mo ntmo r il l o nite
c l a y s o l id is a bento nite c l a y .
1 7 . The p r o c es s o f c l a im 1 6 W her ein s a id bento nite c l a y
is a g el .
1 8 . The p r o c es s o f c l a im 1 2 W her ein s a id demu l s i? er is a n
etho xy l a ted a l c o ho l ha v ing the f o r mu l a :
H H H
0 O ( I)
c H2 CH2
R R X R
W her ein R is s el ec ted f o r m the g r o u p c o ns is ting o f a l k a nes
o r a l k enes f r o m 8 to 2 0 c a r bo ns , E is CH2 — CH2 a nd P is
— CH2 — CH— CH3, n r a ng es f r o m 1 to 5, m r a ng es f r o m 0
to 5 a nd x r a ng es f r o m 3 to 9.
1 9. The p r o c es s o f c l a im 1 W her ein s a id emu l s io n is
s o nic a ted a t a bo u t 2 5 to a bo u t 500 W a tts / c m2 p r io r to s a id
s ep a r a tio n s tep
2 0. The p r o c es s o f c l a im 1 W her ein s a id s ta r ting o il is a
c r u de o il , c r u de o il dis til l a te, c r u de o il bl end o r mixtu r es
ther eo f .
2 1 . The p r o c es s o f c l a im 1 9 W her ein s a id s o nic a tio n is
c o ndu c ted a t f r equ enc ies o f a bo u t 1 5 k HZ to a bo u t 1 0 MHZ.
* * * * *

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