US006955220B2

( 1 2) United States Patent ( 1 0) Patent N 0. 2 US 6, 955, 220 B2

Maberry et al . ( 4 5) D ate o f Patent: O c t. 1 8 , 2005
( 54 ) PRO CESS O F WELL CEMEN TIN G IN CO LD 4 , 93 6, 3 8 4 A * 6/ 1 990 Sugama . . . . . . . . . . . . . . . . . . . . . . 1 66/ 28 3
EN VIRO N MEN T 5, 3 4 0, 3 8 5 A 8 / 1 994 Arf aeietal . 1 06/ 1 4 . 05
5, 3 4 8 , 58 3 A * 9/ 1 994 Arf aei et a1 . . . . . . . . . . . . . . . . 1 06/ 696
( 7 5) Inv ento rs: Jac k Maberry, K aty, TX ( Us) ; Greg 5, 64 1 , 3 52 A * 6/ 1 997 Jeknav o rian et a1 . . . . . . . . 1 06/ 8 08
Garr} so n> K aty TX ( Us) ; Step h an FO REIGN PATEN T D O CUMEN TS
H arris, Mandev il l e, LA ( US) ; Andre
Garnier, K aty, TX ( US) EP 0 554 04 6 8 / 1 993
W0 00 293 51 5/ 2000
( 7 3 ) Assignee: Sc h l umberger Tec h no l o gy
Co rp o ratio n, Sugar Land, TX ( US) O TH ER PUBLICATIO N S
* _ _ _ _ _ CEITEC Ev al uatio n Pl an f o r Lo W Temp erature Co nc rete
( ) N o tl c e: SubJeCt_ tO any dl sc l al mer> _ th e term o f th l s Admix tures ( h ttp : / / WWW. c erf . o rg/ p df s/ c eitec / l o Wtemp /
p atent is ex tended o r adJusted under 3 5 p l anp df ) ac c essed Ap t 25, 2003 4
U' S' C' 1 54 ( k) ) by 0 days Po l arSet Pro duc t Inf o rmatio n bro c h ure, W. R. Grac e and
Co . p ubl ish ed Mar. 2001 . *
( 21 ) Ap p l - N O - I 1 0/ 029, 3 3 3 Po l arSet Material Saf ety D ata Sh eet D ec . 4 , 2001 . *
( 22) Fil ed: D EC. 21 , 2001 > F Cited by ex aminer
( 65) Pno r Pubh c atl o n D ata Primary Ex aminerJo h n K rec k
US 2003 / 01 7 3 08 3 A1 Sep . 1 8 , 2003 ( 7 4 ) Atto rney, Agent, o r FirmD av id Cate; Tim Curingto n;
7 Ro bin N av a
( 51 ) Int. Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E21 B 3 3 / 1 3
( 52) US. Cl . . . . . . . . . . . . . . . . . . . . . . . . 1 66/ 292; 1 66/ 293 ; 1 66/ 901 ; ( 57 ) ABSTRACT
1 06/ 7 1 3
Th e p resent inv entio n p ro v ides imp ro v ed Wel l c ementing
meth o ds f o r use in c o l d env iro nment, Wh ere th e c irc ul ating
temp erature o f th e c ement is typ ic al l y With in th e range o f 5
( 56) Ref erenc es Cited to 20 C. Th e imp ro v ed Wel l c ementing meth o ds inc l ude
f o rmmg c o mp o sitio ns th at are essential l y c o mp rised o f an
US. PATEN T D O CUMEN TS aqueo us ? uid, a h ydraul ic c ement binder and a set
ac c el erating admix ture c o mp rising an al kal i o r al kal ine earth
( 58 ) Fiel d o f Searc h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 66/ 292, 293 ,
1 66/ 294 , 901 ; 1 06/ 7 1 3 , 7 24 , 7 27 , 7 29
3 , 1 7 9, 528 A * 4 / 1 965 H o l mgren et al . . . . . . . . . . . 1 66/ 293 ~ ~ ~ - -
3 , 926, 257 A * 1 2/ 1 97 5 Manast et a1 ~ ~ ~ ~ ~ ~ ~ ~ N 1 66093 metal mtrate and an al kah o r al kal me earth metal nitrite.
4 , 4 8 2, 3 7 9 A * 1 1 / 1 98 4 D ibrel l et al . . . . . . . . . . . . . . . 1 66/ 292
4 , 8 1 8 , 28 8 A * 4 / 1 98 9 Aignesberger et a1 . 1 66/ 293 1 9 Cl aims, 1 D rawing Sh eet
' O " 0. 0gp s + 0. 05gp s + ( l 1 gp s + 0. 1 5gp s + 0. 2gp s + 0. 4 gp s
2000 l
i
I
1
5
1 500 r ?
1 000
Gel Strength ( l bf l 1 00 f t )
U1 0 O
Tl me x 1 0 ( minutes)
U. S. Patent O c t. 1 8 , 2005 US 6, 955, 220 B2
' O ' 0. 0gp s + 0. 05gp s + 0. 1 gp s + 0. 1 5gp s + 0. 2gp s + 0. 4 gp s
2000
1 000
Gel Strength ( l bf l 1 00 1 1 2)
Time x 1 0 ( minutes) FIG 1
1 00
8 0
Co nsistenc y ( Be)
T Y r I I
|
0 4 8 1 2 1 6 20 24 28
Time x 1 0 ( minutes) FIG. 2
US 6, 955, 220 B2
1
PRO CESS O F WELL CEMEN TIN G IN CO LD
EN VIRO N MEN T
FIELD O F TH E IN VEN TIO N
Th e p resent inv entio n rel ates to Wel l c ementing meth o ds
and mo re p artic ul arl y, to c o mp o sitio ns f o r use in c o l d
subterranean env iro nment, as enc o untered f o r instanc e in
deep Water o f f sh o re Wel l s.
BACK GRO UN D O F TH E IN VEN TIO N
Af ter dril l ing a Wel l , suc h as an o il o r gas Wel l , a c asing
is c o mmo nl y l o Wered into th e Wel l bo re. Cement sl urry is
th en p ump ed do Wnh o l e tro ugh th e c asing and bac k up into
th e annul us betWeen th e c asing and th e bo reh o l e. Up o n
setting, th e sl urry f o rms a c ement sh eath th at h o l ds th e
c asing in p l ac e, stabil iZ es and p ro tec ts th e c asing. In
additio n, th e c ement sh eath p ro v ides Z o nal iso l atio n. It is
th us c ritic al to p rev ent up Ward ? uid ? o W, suc h as gas
migratio n o r Water ? o Ws, th ro ugh and al o ng th e c ement
sh eath ? uid and to p rev ent ex c h ange betWeen and amo ng
f o rmatio n l ayers th ro ugh Wh ic h th e Wel l bo re p asses.
H ydraul ic c ements set and dev el o p c o mp ressiv e strength
as a resul t o f h ydratio n o f dif f erent c ement p h ases. Al th o ugh
th is is a c o ntinuo us p ro c ess, th ree main p h ases c an arbi
traril y be de? ned. In th e ? rst p h ase, th e c ement sl urry h as a
rel ativ el y l o W v isc o sity and essential l y c o nstant Th eo l o gic al
p ro p erties. Th is ? rst p h ase c o rresp o nds to th e p ump ing and
p l ac ement o f th e c ement do Wnh o l e. In th e sec o nd p h ase, th e
c o nsistenc y o f th e c ement inc reases so th at it bec o mes
dif ? c ul t to p ump and p l ac e it c o rrec tl y. H o Wev er, th e dev el
o p ed c o mp ressiv e strength is no t eno ugh f o r th e c ement to
be sel f - sup p o rted and to With stand a signi? c ant strength . In
th e th ird and l ast p h ase, th e c ement c o ntinues to dev el o p
c o mp ressiv e strength but th e Wel l sec urity is insured and th e
Wel l c o nstruc tio n may be resumed.
Fro m a gas migratio n p o int o f v ieW, it sh o ul d al so be
no ted th at during th e ? rst p h ase, th e h ydro static p ressure o f
th e h eigh t o f c ement sl urry is h igh eno ugh to c o mp ensate
f o rmatio n gas p ressure. Set c ement is gas- tigh t so th at if th e
p l ac ement o f th e c ement Was adequatel y p erf o rmed, no gas
migratio n sh o ul d o c c ur. H o Wev er, during th e transitio n
p h ase, gas p erc o l atio n With in th e gel l ing sl urry c an o c c ur
unl ess th e c ement sl urry is sp ec i? c al l y designed and
inc l udes f o r instanc e gas migratio n additiv es suc h as l attic es.
Th e sec o nd p h ase- o r transitio n p h aseis th us no t o nl y
essential l y a Waste o f time ( and c o nsequentl y o f mo ney) but
al so a p erio d during Wh ic h th e risk o f a maj o r ac c ident suc h
as a bl o W- o f f is at its max imum. Th is is Wh y so - c al l ed
Righ t- Angl e- Set ( RAS) c ements h av e rec eiv ed p artic ul ar
attentio n. RAS c ement sl urries are de? ned as Wel l - disp ersed
systems th at sh o W no gel atio n tendenc y and set v ery rap idl y
due to rap id h ydratio n kinetic s; in o th er Wo rds, RAS sl urries
ex h ibit a v ery sh o rt transitio n time.
D ue to c ement h ydratio n kinetic s, designing RAS sl urries
f o r temp eratures bel o W 1 20 C. is dif f ic ul t. Th e c o o l er th e
temp erature, th e l o nger th e c ement set. Th eref o re, it is
esp ec ial l y dif ? c ul t to design a c ement sl urry suitabl e f o r c o l d
env iro nment suc h as o f f sh o re Wel l s. In deep Water Wel l s,
temp eratures at seabo tto m are as l o W as abo ut 4 C. , and
ev en l o Wer in arc tic Z o nes so th at th e c irc ul ating temp erature
o f th e c ement typ ic al l y ranges betWeen 4 C. and 20 C.
Th is p ro bl em o f l o W temp erature h as been addressed by
dev el o p ing f o rmul atio ns based o n sp ec i? c h ydraul ic bind
ers. Th ese f o rmul atio ns are essential l y div ided into two
1 0
1 5
25
3 5
4 0
4 5
55
65
2
c l asses: f o rmul atio ns based o n gyp sum ( Pl aster) o r mo re
ex ac tl y o n gyp sum/ Po rtl and c ement bl end and f o rmul atio ns
based o n al umino us c ement. Th e p erf o rmanc e o f al umino us
c ements migh t be sev erel y af f ec ted by c o ntaminatio n With
Po rtl and c ements and c o nsequentl y, th ey must be sto red in
sep arate sil o s. Th eref o re, due to l o gistic al reaso ns, f o rmu
l atio ns based o n p l aster h av e rec eiv ed mo re attentio n.
N ev erth el ess, it Wo ul d be desirabl e to be abl e to use mo re
c o nv entio nal and l ess ex p ensiv ef o rmul atio ns simil ar to
th o se used f o r c ementing th e deep er p art o f th e Wel l , Wh ic h
are subj ec t to h igh er temp erature due to th e th ermal geo desic
gradient.
Ac c o rding to standard p rac tic e, c ement sl urries are usu
al l y f o rmul ated With c o nv entio nal additiv es inc l uding f o r
instanc e set retarders o r set ac c el erato rs, disp ersing agent
and ? uid l o ss c o ntro l additiv es. As desc ribed, f o r ex amp l e,
in Wel l Cementing, edited by E. I. N el so n, Sc h l umberger
Educ atio nal Serv ic es ( 1 990) , an ac c el erating ac tio n h as been
rep o rted f o r many ino rganic sal ts inc l uding c h l o rides,
c arbo nates, sil ic ates, al uminates, nitrates, nitrites, sul f ates,
th io sul f ates and al kal ine bases suc h as so dium, p o tassium
and ammo nium h ydro x ydes. Amo ng th ese, c al c ium c h l o ride
is by f ar th e mo st c o mmo n set ac c el erato r used f o r Po rtl and
c ement.
H o Wev er, c al c ium c h l o ride h as sev eral side ef f ec ts th at
are no t bene? c ial . Cal c ium c h l o ride af f ec ts th e rh eo l o gic al
p ro p erties o f th e sl urry resul ting in an inc rease o f th e
v isc o sity. Cal c ium c h l o ride al so h as a deterrent imp ac t as to
th e p ermeabil ity o f th e set c ement. Lo Wer p ermeabil ity is no t
desirabl e in c o ntro l l ing gas migratio n and th e resistanc e o f
th e c ement to sul f ate brines is dec reased.
Vario us o th er additiv es o r c o mbinatio ns o f kno wn addi
tiv es h av e been dev el o p ed f o r th e c o nstruc tio n industry,
aiming at p ro v iding mo rtars to al l o W c o nc rete p l ac ement at
ambient temp erature under c o l d o r sub f reeZ ing Weath er. In
p artic ul ar, c h l o ride- f ree set- ac c el erating admix tures, based
o n al kal i o r al kal ine earth metal sal t nitrate, nitrite, f o rmate
o r ac etate, h av e been c o mmerc ial iZ ed. H o Wev er, it is Wel l
kno Wn th at Wel l c ementing ex p o ses Po rtl and c ement to
c o nditio ns f ar dif f erent f ro m th o se enc o untered in c iv il
engineering Wh ere th e sp ec i? c atio ns With regard to rh eo
l o gic al p ro p erties, gas migratio n c o ntro l and ? uid l o ss
c o ntro l are absent o r at l east dramatic al l y dif f erent.
It is th us an o bj ec t o f th e p resent inv entio n to p ro v ide neW
Wel l c ementing f o rmul atio ns th at set rap idl y at l o Wer
temp eratures, i. e. bel o W 20 C. and mo re p ref erabl y bel o W
1 0 C. , and th at sh o W sup erio r p erf o rmanc e o v er th e p rio r art
f o rmul atio ns.
SUMMARY O F TH E IN VEN TIO N
Th e p resent inv entio n p ro v ides imp ro v ed Wel l c ementing
c o mp o sitio ns f o r use in c o l d env iro nment, Wh ere th e c irc u
l ating temp erature o f th e c ement is typ ic al l y With in th e range
o f abo ut 5 C. to abo ut 20 C. Th e imp ro v ed Wel l c ementing
c o mp o sitio ns are essential l y c o mp rised o f an aqueo us ? uid,
a h ydraul ic c ement binder and a set- ac c el erating admix ture
c o mp rising an al kal i o r al kal ine earth metal nitrate and an
al kal i o r al kal ine earth metal nitrite.
Th e inv entio n inv o l v es th e use o f an admix ture o f nitrate
and nitrite sal t to enh anc e gel strength and c o mp ressiv e
strength dev el o p ment. Cal c ium sal ts are p artic ul arl y p re
f erred. Aratio o f abo ut 1 : 1 is p ref erred but a range o f Weigh t
ratio s o f f ro m abo ut 1 : 3 to abo ut 3 : 1 may be used. Th e
mix ture is usual l y added as a l iquid additiv e, th e sal ts being
mix ed in Water to p rep are th e l iquid.
Th e set- ac c el erating c o ntro l additiv e may f urth er be f o r
mul ated to inc l ude l o W mo l ec ul ar Weigh t gl yc o l s suc h as C2
US 6, 955, 220 B2
3
to C6 al ip h atic di- and tri- h ydric gl yc o l s suc h as eth yl ene
gl yc o l , dieth yl ene gl yc o l , p ro p yl ene gl yc o l and gl yc ero l f o r
instanc e. Th e gl yc o l is typ ic al l y added into th e admix ture in
th e range o f 0 and 3 0 Weigh t p erc ent, mo st p ref erabl y
betWeen abo ut 5 and abo ut 1 5 Weigh t p erc ent, based o n th e
to tal Weigh t o f so l ids in th e admix ture.
Ac c o rding to a p ref erred embo diment, th e set ac c el erating
c o ntro l additiv e o f th e p resent inv entio n may al so c o mp rise
at l east a di- o r tri- h ydro x yal kyl amine. Partic ul arl y p re
f erred are al kano l amine o f th e f o rmul a:
R2
Wh ere R1 and R2 are h ydro x yal kyl gro up s in C1 C4 , and R3
is a C1 C5 al kyl gro up s, suc h as meth yl o r eth yl dieth ano
l amine. Th e amo unt o f al kano l amine p ref erabl y ranges
betWeen 0 and 6 Weigh t p erc ent, based o n th e to tal Weigh t
o f so l ids in th e admix ture, and mo st p ref erabl y, betWeen 2
and 4 Weigh t p erc ent.
Th e f o rmul atio n may al so c o mp rise mino r amo unts o f
o th er al kal i o r al kal ine earth metal sal ts suc h as al kal i o r
al kal ine earth metal c h l o ride, bro mide, io dide, c yanide,
sil ic ate and h ydro x ide, and in p artic ul ar, a mino r amo unt o f
c al c ium bro mide.
Ac c o rding to a mo st p ref erred embo diment o f th e p resent
inv entio n, th e set admix ture o f th e p resent inv entio n c o nsists
o f c al c ium nitrate, c al c ium nitrite, dieth yl ene gl yc o l , meth
yl dieth ano l amine and c al c ium bro mide in a p ro p o rtio n o f
4 224 221 03 23 by Weigh t in Water, With a so l id c o ntent
betWeen 4 5 and 50%.
Th e set admix ture is typ ic al l y added to th e c ement c o m
p o sitio n in an amo unt th at p ro v ides a sal t c o nc entratio n
( essential l y c al c ium nitrate and c al c ium nitrite as ex p l ained
abo v e) betWeen abo ut 3 and abo ut 20 g p er kg o f c ement.
With th e p ref erred f o rmul atio n mentio ned abo v e, th is resul ts
in c o nc entratio n o f th e set- admix ture ranging betWeen abo ut
4 and abo ut 4 5 c m3 p er kg o f c ement.
Th e term h ydraul ic c ement binder as used h erein ref ers
to any c l ass o f API Po rtl and c ement as de? ned by th e
Americ an Petro l eum Institute ( API) With th e ex c ep tio n o f
th e c l asses D , E and F intended f o r use under h igh temp era
tures and any o f th e typ es I, II, III and V de? ned by th e
Americ an So c iety f o r Testing and Material s ( ASTM) . Sp e
c ial grinds o f c ement suc h as mic ro ? ne c ement and ? ne
grind l igh tWeigh t typ e c ements and/ o r sh al e mix tures may
be used.
In c o ntrast to so me c o nv entio nal f o rmul atio ns, any suit
abl e aqueo us ? uid may be used as mix ing Water. As used
h erein, th e p h rase aqueo us ? uid is understo o d to inc l ude
f resh Water, sal t Water, seaWater, o r brine. Th e aqueo us ? uid
is p resent in th e c o mp o sitio n in an amo unt suf ? c ient to f o rm
a sl urry th at c an be p ump ed do Wnh o l e. Typ ic al c o nc entra
tio ns o f aqueo us ? uid may range f ro m 3 0 to 1 00% by Weigh t
o f c ement. General l y, th e amo unt o f aqueo us ? uid is suc h
th at th e density o f th e sl urry ranges betWeen abo ut 0. 9 and
3 g/ c m3 [ abo ut 8 and 25 p p g ( p o unds p er gal l o n) ] , and mo st
typ ic al l y betWeen 1 2 and 1 6. 4 p p g. Fo r l o Wer density, i. e. in
th e 8 to 1 2 p p g range, th e f o rmul atio n ac c o rding to th e
inv entio n may be f o amed by th e additio n o f suitabl e f o am
ing agents, f o am stabil iZ ing agents and an inert gas suc h as
nitro gen and/ o r air. Co nc entratio ns o f f o aming agents range
general l y f ro m abo ut 0. 5% to abo ut 5% by Weigh t o f
c o mp o sitio n ? uid; f o am stabil iZ ing agents range f ro m abo ut
0. 5 to 5% by Weigh t o f th e c o mp o sitio n ? uid; and c o nc en
1 5
25
3 5
4 0
4 5
55
65
4
tratio ns o f gas ranging f ro m 1 0% to 60% o f to tal v o l ume o f
? nal f o amed sl urry v o l ume.
Th e Wel l c ementing c o mp o sitio ns o f th e p resent inv entio n
may al so inc l ude o th er additiv es suc h as ? uid l o ss c o ntro l
additiv es, gas migratio n c o ntro l additiv es, disp ersants, and
o th er additiv es c o mmo nl y used in c ement sl urries. Ex amp l es
o f ? uid l o ss and gas c o ntro l additiv es inc l ude deriv atio ns o f
p o l yv inyl al c o h o l , p o l yv inyl p yrro l ido ne, and l atex p o l ymer
disp ersio ns suc h as c o p o l ymers o f styrene and butadiene.
Typ ic al c o nc entratio ns f o r suc h additiv es c an range f ro m
abo ut 0. 1 % to 4 % by Weigh t o f c ement. D isp ersants are used
to reduc e th e sl urry v isc o sity and al l o W th e c ement to l o Wer
th e Water requirement f o r mix ing th e c ement. Typ ic al c o n
c entratio ns range f ro m abo ut 0. 01 % to 1 % by Weigh o f
c ement. Ex amp l es o f disp ersants inc l ude so dium nap h th a
l ene sul f o nate o r p o l ymel amine sul f o nates.
Th e Wel l c ementing c o mp o sitio ns o f th e p resent inv entio n
are ex tremel y adv antageo us Wh en used in c o l d env iro nment
suc h as o f f sh o re Wel l s in deep Water ( 600 m bel o W th e
sea? o o r) , Wh ere th e p l ac ement temp erature typ ic al l y range
f o rm abo ut 5 C. to abo ut 20 C.
BRIEF D ESCRIPTIO N O F TH E D RAWIN GS
Th e abo v e and f urth er o bj ec ts, f eatures and adv antages o f
th e p resent inv entio n Wil l be better understo o d by ref erenc e
to th e ap p ended detail ed desc rip tio n, and to th e draWings
Wh erein:
FIG. 1 sh o Ws th e gel strength dev el o p ment at 65 F. , as a
f unc tio n o f time, o f c ement c o mp o sitio ns c o mp rising v ari
o us c o nc entratio n o f th e set- ac c el erativ e mix ture o f th e
p resent inv entio n;
FIG. 2 sh o Ws th e c o nsistenc y dev el o p ment at 65 F. , as a
f unc tio n o f time, o f a c ement c o mp o sitio n ac c o rding to th e
p resent inv entio n and o f a c o mp o sitio n ac c o rding to th e
p rio r art.
D ESCRIPTIO N O F PREFERRED
EMBO D IMEN TS
Th e f o l l o Wing ex amp l es il l ustrate th e inv entio n With o ut
l imiting its sc o p e.
EXAMPLE 1
Initial Ev al uatio n
Vario us c ement c o mp o sitio ns Were p rep ared util iZ ing
l igh tWeigh t c ement and c o mmerc ial ac c el erato rs used f o r th e
c o nstruc tio n industry. Th e tested c ement av ail abl e f ro m
TXI, United States and is p ro duc ed by intergrinding Po rt
l and c ement and a l igh tWeigh t sh al e aggregate and h as
p ro v en to be suitabl e f o r o il and gas Wel l o p eratio ns in deep
Water.
Th e Water c o ntent Was adj usted to ac h iev e a density o f
1 251 0. 1 l bs. p er gal l o n ( 1 2. 5 p p g= 1 . 4 98 g/ c m3 ) . Fo r th is
initial sc reening, sev eral ac c el erato rs Were subj ec ted to a
ro und o f tests to determine th e c o mp ressiv e strength
ac h iev ed af ter 8 h o urs using 2 inc h es- mo l ded c ubes c ured in
a 1 00% h umidity c h amber at ro o m temp erature
( ap p ro x imatel y 7 5 F. o r 24 C. ) . Th e c o nc entratio n o f
ac c el erato r is in gal l o ns p er sac k o f c ement ( i. e. , 0. 1 US
gal l o ns ( 3 . 7 8 l iters) p er 4 2 kil o gram sac k, 0. 1 gp s= 9 c m3 / kg
o f c ement) . Th is c o nc entratio n Was based o n th e ac tiv e
c ement c o ntent o f th e TXI Ligh tWeigh t c ement, ex c l uding
th e inert l igh tWeigh t aggregate. Th e tests Were c arried o ut
using, c al c ium c h l o ride, so l utio ns o f nitrate and/ o r nitrite
sal ts, and no set additiv e. Based o n th e Material Saf ety D ata
US 6, 955, 220 B2
5
Sh eet p ro v ided by th e sup p l ier, it is assumed th at th e
c o nc entratio ns o f sal ts in additiv e B, C and D are resp ec
tiv el y 4 0% ( 20+ 20) , 3 0% and 4 5% ( by Weigh t) . Th e resul ts
are sh o Wn in tabl e 1 .
5
TABLE 1
8 h r
Ad- Ch emic al Co mp o sitio n Co mp ressiv e Strength
ditiv e ( by Weigh t) Co nc entratio n at Ambient Temp erature
1 0
N o ne Set With no
measurabl e strength 4
A 3 2% Cal c ium Ch l o ride 0. 265 gal / sk 3 8 p si
B1 Cal c ium nitrate <20% 0. 1 51 gal / sk 1 5 p si
Cal c ium nitrite <20%
Cal c ium Bro mide <2% 1 5
D ieth yl ene gl yc o l <5%
Meth yl ene
dieth ano l amine <2%
B Meth yl ene- 0. 3 02 gal / sk 7 8 p si
dieth ano l amine <2%
C2 Cal c ium N itrite > 3 0% 0. 08 gal / sk 4 p si 20
C " 0. 6 gal / sk 1 7 p si
D 3 Cal c ium nitrate <4 5% 0. 1 4 1 gal / sk Set With no
measurabl e strength 4
1 Av ail abl e f ro m W. R. Grac e & Co . Cambridge, Massac h usetts, under
th e name Po l arset TM
2Av ail abl e f ro m W. R. Grac e & Co . Cambridge, Massac h usetts, under 25
th e name D CI
3 Av ail abl e f ro m W. R. Grac e & Co . Cambridge, Massac h usetts, under
th e name Gil c o Ac c el erato r
4 Th e c ube c an be remo v ed f ro m th e mo l d but th e strength nec essary to
break it is no t suf ? c ient to c ause a de? ec tio n o f th e dial .
Th e so l utio n c o mp rising bo th c al c ium nitrate and c al c ium 3
nitrite sh o Ws greater ac c el eratio n th an is o bserv ed With
c al c ium c h l o ride. N eith er th e so l utio n c o mp rising c al c ium
nitrate no r th e so l utio n c o mp rising c al c ium nitrite p ro v ided
any signi? c ant c o mp ressiv e strength .
Admix ture C o f ex amp l e 1 Was f urth er ex tensiv el y tested
to ev al uate its suitabil ity f o r Wel l c o mp l etio n at l o W
temp eratures, inc l uding its c o mp atibil ity With standard addi
tiv es. Unl ess o th erWise indic ated, al l tests f o l l o Wed rec o m
mended p rac tic es o utl ined in API RP 1 0 B.
Fo r th ic kening times th e c o nsisto meter c h amber Was Z / 3
? l l ed With o il and p rec h il l ed to ap p ro x . 65 F. Th e sl urry Was
mix ed as p er standard API p ro c edure, p o ured into th e
c o nsisto meter c up and p l ac ed in th e c h il l ed c h amber. Th e l id
Was c l o sed and th e c h amber to p p ed o f f With o il . Th e sl urry
Was stirred at 1 50 rp m With a p ressure o f 1 500 p si ap p l ied.
Th e c h il l er Was adj usted to bring th e sl urry do Wn to 65 F.
as quic kl y as p o ssibl e ( usual l y 1 0 to 20 minutes) and th en
readj usted to maintain th e sl urry at 65 F. until th e sl urry set.
Fo r testing th e c o mp ressiv e strength , th e c o o l ing Water
l ines f o r th e Ul tra So nic Cement Anal yZ er ( U. C. A. ) Were
attac h ed to a c h il l er. Th e c el l Was p rec h il l ed in th e l ab
ref rigerato r to ap p ro x . 55 F. ( 1 2. 7 C. ) and th e UCA
c h amber Was al so p rec h il l ed to 55 F. Th e sl urry Was mix ed
as p er API, p ut in th e c el l , l o Wered into th e UCA and
p ressuriZ ed to 1 500 p si ( 1 0. 3 4 MPa) . Again th e c h il l er s
temp erature Was adj usted to bring th e sl urry do Wn to 55 F.
as quic kl y as p o ssibl e ( usual l y 1 0 minutes) and th en read
j usted to maintain a temp erature o f 55 F. Th e test duratio n
Was 24 o r 4 8 h o urs. Th e th ic kening time c o rresp o nds to th e
p ro duc tio n o f a c o nsistenc y o f 1 00 BC, measured in stan
dardiZ ed BC units. Th e transitio n time c o rresp o nds to p ass
ing f ro m a c o nsistenc y o f 3 0 BC to a c o nsistenc y o f 1 00 BC.
A sh o rt transitio n time is desirabl e. Th e time required to
attain a c o mp ressiv e strength o f 50 p si ( 3 4 5 kPa) and 500 p si 65
( 3 4 50 kPa) Was measured, as Wel l as th e c o mp ressiv e
strength af ter 24 h o urs.
3 5
4 0
4 5
50
6
Rh eo l o gies Were p erf o rmed ac c o rding to th e standard API
p ro c edures, j ust af ter mix ing and With sl urries c o nditio ned
f o r 20 minutes at 8 0 F. Th e measured data inc l ude p l astic
v isc o sity ( in mil l ip asc al s sec o nd o r c entip o ises) and th e
yiel d p o int, ex p ressed as is c usto mary in th e art in l bf / f t2.
Co mp o sitio ns With l o W v isc o sity and l o W yiel d p o int are
desirabl e. Measurements Were al so c arried o ut o n th e gel
strength dev el o p ed Wh en th e c o mp o sitio n is l ef t to rest f o r
1 0 minutes.
Th e ? uid l o ss o f th e sl urries Was measured af ter 3 0
minutes, ac c o rding to standard API p ro c edures. Val ues
bel o W 1 00 ml , p ref erabl y bel o W 50 ml , are asso c iated With
l o Wer risks o f gas migratio ns and th eref o re are desirabl e.
Th e v ane rh eo meter p ro c edure f o l l o Ws: af ter p rec h il l ing
th e c el l , senso r Z ero ing and f ric tio n testing th e v ane rh eo m
eter; th e sl urry Was mix ed and p l ac ed in th e c el l . Th e mo to r
sp eed f o r th e v ane rh eo meter Was set at 0. 1 rp m and th e test
c ut o f f gel strength Was th e def aul t setting o f 1 550 l bf / 1 00
f t2 ( 0. 07 MPa) . A p ressure o f ap p ro x imatel y 4 00 p si ( 2. 7 5
MPa) Was ap p l ied to th e sl urry and th e test Was initiated.
Again th e c el l Was rap idl y c o o l ed to temp erature ( usual l y 20
to 3 0 minutes) and th e c h il l er s c o ntro l l er readj usted to
maintain th e desired temp erature. Fo r th e 4 5 F. tests th e c el l
Was c h il l ed in th e f reeZ er f o r 1 5 minutes in o rder to quic kl y
reduc e it s temp erature to th e desired l ev el .
Unl ess o th erWise sp ec i? ed, al l tests bel o W Were c arried
0 o ut using th e set- admix ture B ac c o rding to th e p resent
inv entio n.
EXAMPLE 2
Co mp ariso n With Co nv entio nal Ac c el erato rs
Cement sl urries With a density o f 1 6. 4 p p g ( 1 . 96 g/ c m3 ) ,
c o mp rising a gas c o ntro l additiv e, a disp ersing agent and a
set c o ntro l additiv e ( th e admix ture o f th e p resent inv entio n
o r c al c ium c h l o ride, eith er under l iquid o r so l id f o rm) Were
p rep ared With a Cl ass H c ement.
Th e rh eo l o gy o f th e sl urry and th e setting p ro p erties are
sh o Wn in tabl e 2.
TABLE 2
Gas c o ntro l additiv e ( gal / sk) 0. 4 0. 5
D isp ersant ( gal / sk) 0. 04 0. 06
Set c o ntro l additiv e ( gal / sk) 0. 4 0. 2
Liquid CaCl 2 ( gal / sk) 0. 4
CaCl 2 ( % BWO C) _ _ _ 1 2
Rh eo l o gy Af ter mix ing
PV ( 0P) 4 5 4 7 4 9 55 8 6
TY ( l bf / l O O a2) 1 2 9 3 3 22
Rh eo l o gy at 8 0 F.
PV ( 0P) s9 59 53 90
TY ( l bf / l O O a2) 24 1 6 5 1 2
1 0 minutes gel ( l bf / l O O a2) 3 2 3 7 26
Th ic kening Time at 55 F. and 3 : 58 3 : 1 8 4 : 25 6: 00 4 : 1 2
1 500 p si ( h r: min)
Initial c o nsistenc y ( Bc ) 22 1 8 1 7 1 9 20
Time 3 0- 1 00 Bc ( h r: min) 2: 4 2 1 : 53 1 : 4 3 3 : 22 2: 4 1
UCA at 55 F. and 1 500 p si
Time to reac h 50 p si ( h r: min) 7 : 3 5 N / A 6: 4 7
Time to reac h 500 p si ( h r: min) 1 5: 4 7 N / A 1 6: 22
Co mp ressiv e strength at 24 h rs 1 01 0 261 8 62
( Psi)
US 6, 955, 220 B2
7
TABLE 2- c o ntinued
8
additiv e o f th e p resent inv entio n. As sh o wn in Tabl e 4 bel o w,
th e sl urry may be p rep ared eith er in f resh o r seaWater.
API Fl uid Lo ss at ro o m temp . 1 9 1 8 1 4 1 9
( mL/ 3 0 min. ) TABLE 4
Vane rh eo rneter test at 65 F. and 5
4 00 PSi Mix ing Water Fresh Sea
Time to reac h 1 550 p si ( h r: min) 2: 3 0 2: 20 _ _
Time f ro m 1 00 to 500 l bf / l O O f t2 7 0 95 Rh eo l o gy Af ter 1 1 mg
( min)
1 0 PV ( CP) 4 9 51
_ _ _ _ TY ( 1 bf / 1 O O a2) 3 1 6
Th is sh o Ws th at th e set- admix ture o f th e p resent inv entio n Rh e O 1 0 gy at 8 00 E
c an be used in Wel l c ementing f o rmul atio ns, ( c o l umn 2 and
3 ) , ac c el erates c ement h ydratio n and resul ts in reduc ed gel PV ( GP) 53 61
times and earl y c o mp ressiv e strength , signi? c antl y 1 5 TY ( bf / 1 00 f tz ) 5 1 7
imp ro v ed o v er th e p rio r art f o rmul atio ns based o n c al c ium 1 0 minutes gel ( El f / 1 00 f tz ) 22
c h l o ride. In additio n, With th e set- admix ture o f th e p resent Th ic kening Time at 550 E and 1 500 p si ( h rz min) 4 : 25 4 : 1 7
inv entio n, th e sl urry rh eo l o gy is no t signi? c antl y af f ec ted Initial c o nsistenc y ( BC) 1 7 1 8
With inc reased c o nc entratio ns. O n th e o th er h and, inc reased Time 3 O _ 1 O O BC ( h nmin) 1 . 4 3 1 . 53
c o nc entratio ns o f c al c ium c h l o ride resul t in no n- desirabl e 2O UCA at 550 E and 1 500 p si
inc reased v isc o sity.
E PLE 3 Time to reac h 50 p si ( h r: min) 7 : 3 5 7 : 4 3
Time to reac h 500 p si ( h r: min) 1 5: 4 7 1 5: 53
. . . C ' t th t 24 h ' 1 01 0 1 23 1
Ef f ec t o f th e Co nc entratio n o f th e Set Additiv e o mp ref swe S reng a rs ( p s1 ) _
. . 25 API Fl uid Lo ss at ro o m temp . ( mL/ 3 0 min. ) 1 4
Mix ed With Fresh Water 0 .
Vane rh eo rneter test at 65 F. and 4 00 p si
Cement sl urries With a density o f 1 6. 4 p p g ( 1 . 96 g/ c m3 ) ,
Were p rep ared With a Cl ass H Po rtl and c ement. Al l f o rmu- Time to reac h 1 550 Psi ( h rimin) 21 3 0 21 20
l atio ns c o mp rise a gas c o ntro l additiv e ( 0. 5 gal / sk) , a dis- Time f ro m 1 00 to 5001 bf / 1 00 f t2 ( min) 7 0 67
p ersing agent ( 0. 06 gal / sk) and th e set c o ntro l additiv e o f th e 3 0
p resent inv entio n at v ario us c o nc entratio ns.
TABLE 3
Set c o ntro l additiv e ( gal / sk) 0 0. 05 0. 1 0. 1 5 0. 2 0. 3 0. 4
Rh eo l o gy Af ter mix ing
PV ( GP) 52 62 4 9 55 55
TY ( 1 bf / 1 O O a2) 5 4 3 4 4
Rh eo l o gy at 8 0 F.
PV ( GP) 4 7 64 53 59 7 2
TY ( 1 bf / 1 O O a2) 7 5 5 1 2 3
1 0 minutes gel ( l bf / 1 00 f tz ) 1 4 8 3 8 1 4
Th ic kening Time at 55 F. and 1 500 p si ( h r: min) 1 0: 1 0 8 : 27 7 : 27 5: 3 1 4 : 25 3 : 3 8 2: 55
Initial c o nsistenc y ( Bc ) 1 2 20 1 2 25 1 7 1 2 1 0
Time 3 0- 1 00 Bc ( h r: min) 3 : 3 9 3 : 1 7 2: 03 2: 29 1 : 4 3 1 : 23 1 : 1 0
UCA at 55 F. and 1 500 p si
Time to reac h 50 p si ( h r: min) 1 5: 50 1 3 : 4 2 1 0: 1 7 8 : 56 7 : 3 5 6: 3 4 5: 4 6
Time to reac h 500 p si ( h r: min) N / A N / A 1 8 : 4 3 1 7 : 1 2 1 5: 4 7 1 4 : 04 1 2: 4 0
Co mp ressiv e strength at 24 h rs ( p si) 3 1 5 4 8 4 97 3 1 050 1 01 0 98 5 991
API Fl uid Lo ss at ro o m temp . ( mL/ 3 0 min. ) 1 4
Vane rh eo rneter test at 65 F. and 4 00 p si
Time to reac h 1 550 p si ( h r: min) 6: 20 5: 1 0 4 : 1 0 3 : 3 0 2: 3 0 2: 00 1 : 3 0
Time f ro m 1 00 to 500 1 bf / 1 00 f t2 ( min) 1 61 1 3 6 8 3 8 O 7 0 66 4 7
55
Tabl e 3 , and FIG. 1 , sh o W th at gel strength transitio n time EXAMPLE 5
dec reases With inc reasing c o nc entratio n o f th e set admix
ture' Ef f ec t o f th e Fl uid Lo ss Co ntro l Additiv e
60 . . .
EXAMPLE 4 Cement sl urries With a density o f 1 6. 4 p p g ( 1 . 96 g/ c m)
_ _ Were p rep ared With a Cl ass H Po rtl and c ement. Th e f o rmu
Ef f ec t o f th e Mix ing Water - - - - -
l atio ns c o mp rise a disp ersing agent and a ? uid l o ss c o ntro l
Cement sl urries With a density O f 1 6. 4 p p g ( 1 . 96 g/ c m3 ) additiv e ( a gas c o ntro l additiv e being a ? uid l o ss c o ntro l
Were p rep ared With a Cl ass H Po rtl and c ement. Al l f o rmu- 65 addl tl v e) AS Sh O WIl In Tabl e 5 bel O W, th e sl urry p ro p erties
l atio ns c o mp rise a gas c o ntro l additiv e ( 0. 5 gal / sk) , a dis
p ersing agent ( 0. 06 gal / sk) and 0. 2 gal / sk o f th e set c o ntro l
are no t imp ac ted by th e p resenc e o f a ? uid l o ss c o ntro l
additiv e.
US 6, 955, 220 B2
TABLE 5
Set c o ntro l additiv e ( gal / sk) 0. 2 0. 2 0. 2 0. 4 0. 4
D isp ersant A ( gal / sk) 0. 06 0. 06 0. 06 0. 04 0. 04
Gas c o ntro l additiv e ( gal / sk) 0. 5 0. 4
Fl uid l o ss c o ntro l additiv e ( gal / sk) 0. 5
Rh eo l o gy Af ter mix ing
PV ( CP) 58 4 9 3 3 4 7 3 4
TY ( l bf / l O O n2) 4 3 1 . 4 9 4
Rh eo l o gy at 8 0 F.
PV ( CP) 59 53 4 1 59 4 1
TY ( l bf / l O O n2) 2 5 4 1 6 1 4
1 0 minutes gel ( l bf / 1 00 f t2) 1 2 3 7 27
Th ic kening Time at 55 F. and 1 500 p si ( h r: min) 4 : 4 5 4 : 25 4 : 1 8 3 : 1 8 3 : 29
Initial c o nsistenc y ( Bc ) 20 1 7 24 1 8 1 6
Time 3 0- 1 00 Bc ( h r: min) 1 : 4 8 1 : 4 3 1 : 21 1 : 53 1 : 51
UCA at 55 F. and 1 500 p si
Time to reac h 50 p si ( h r: min) 7 : 56 7 : 3 5 5: 4 7
Time to reac h 500 p si ( h r: min) 1 5: 4 8 1 5: 4 7 1 3 : 1 7
Co mp ressiv e strength at 24 h rs ( p si) 1 08 7 1 01 0 1 3 92
API Fl uid Lo ss at ro o m temp . ( mL/ 3 0 min. ) 3 1 1 4 1 8 7 8 4
Vane rh eo rneter test at 65 F. and 4 00 p si
Time to reac h 1 550 p si ( h r: min) 2: 20 2: 3 0 2: 00
Time f ro m 1 00 to 500 l bf / 1 00 f t2 ( min. ) 53 7 0 52
Th e c o mp o sitio ns o f th e p resent inv entio n are c o mp atibl e
With c o nv entio nal gas c o ntro l additiv es and ? uid l o ss c o ntro l TABLE 6
additiv es, Wh ic h c o ntribute to minimal set retarding ef f ec ts.
3 0 BH CT 55 F. 8 0 F. 1 3 0 F.
Th ic kening Time at 1 500 p si ( h r: min) 4 : 25 2: 1 5 1 : 4 8
Time 3 0- 1 00 Bc h r: rnin 1 : 4 3 0: 3 0 0: 20
EXAMPLE 6 ( )
3 5
EXAMPLE 7
Ef f ec t o f th e Temp erature
Cement sl urries With a density o f 1 6. 4 p p g ( 1 . 96 g/ c m3 )
Were p rep ared With a Cl ass H Po rtl and c ement. Th e f o rmu- 4 0
l atio ns c o mp rise a disp ersing agent and a ? uid l o ss c o ntro l
additiv e at c o nstant c o nc entratio n. As sh o Wn in Tabl e 6
bel o W, inc reasing temp erature p ro v ides dec reased time
between 3 0 and 1 00 Bc . Th e th ic kening time is al so reduc ed
With inc reased temp erature.
Tests With Cl ass A Cement
Tests simil ar to th o se p erf o rmed With Cl ass H c ement
Were c arried o ut using a Po rtl and Cl ass A c ement. Sl urries
With a density o f 1 5. 6 p p g ( 1 . 8 6 g/ c m3 ) , Were p rep ared
inc l uding a disp ersing agent and a ? uid l o ss c o ntro l additiv e
at c o nstant c o nc entratio n. Resul ts are sh o Wn in Tabl e 7
bel o W.
TABLE 7
Set c o ntro l additiv e ( gal / sk) 0 0. 1 0. 2 0. 3 0. 4
Th ic kening Time at 65 F. and 1 500 p si ( h r: min) 8 : 3 1 5: 03 4 : 1 5 4 : 1 1 3 : 58
Initial c o nsistenc y ( Bc ) 1 8 25 1 8 1 8 1 6
Transitio n Time 3 01 00 Bc ( h r: min) 4 : 27 2: 21 1 : 51 2: 01 1 : 4 4
UCA at 55 F. and 1 500 p si
Time to reac h 50 p si ( h r: min) 1 3 : 3 7 1 0: 00 7 : 1 2 5: 4 0 5: 3 0
Time to reac h 500 p si ( h r: min) 22: 3 1 1 6: 21 1 3 : 3 8 1 0: 50 1 0: 4 0
Co mp ressiv e strength at 24 h rs ( p si) 661 1 1 7 0 1 3 3 3 1 3 4 3 1 3 1 8
Vane rh eo rneter test at 65 F and 4 00 p si
Time to reac h 1 550 p si ( h r: min) 3 : 4 0 2: 4 0
Time f ro m 1 00 to 500 l bf / 1 00 f t2 ( min. ) 61 4 3
US 6, 955, 220 B2
1 1
Th e set c o ntro l additiv e o f th e p resent inv entio n is c o m
p atibl e With Cl ass A c ement, as Wel l as With Cl ass H and
Cl ass G c ement typ ic al l y used f o r Wel l c ementing.
EXAMPLE 8
Gel Strength D ev el o p ment
FIG. 2 sh o Ws a p l o t o f th e dev el o p ment o f c o nsistenc y at
65 F. as a f unc tio n o f time f o r a c ement c o mp o sitio n
ac c o rding to th e p resent inv entio n ( ? l l ed c irc l e marks) and
ac c o rding to th e p rio r art, using c al c ium c h l o ride as set
ac c el erato r ( o p en square marks) . Bo th c o mp o sitio ns h av e
been f ul l y o p timiZ ed and c o mp rise a ? uid l o ss c o ntro l agent
and a disp ersing agent. Th e sl urry density f o r bo th c o mp o
sitio ns is 1 6. 4 p p g ( 1 . 96 g/ c m3 ) .
Ev en th o ugh bo th set ac c el erato rs p ro v ide abo ut th e same
th ic kening time, th e c o mp o sitio ns o f th e p resent inv entio n
p resent a muc h righ t- angl e p ro ? l e, Wh ic h is ex tremel y
adv antageo us in reduc ing th e risk o f gas migratio n.
EXAMPLE 9
Co mp ressiv e Strength o f Fo amed Sl urries
A base sl urry h av ing a density o f 1 6. 4 p p g ( 1 . 96 g/ c m3 )
Was p rep ared With a Cl ass H Po rtl and c ement. Th e c o mp o
sitio n is o p timiZ ed f o r Wel l c ementing and c o mp rises a ? uid
l o ss c o ntro l additiv e, a disp ersing agent, a f o aming agent
and a f o am stabil iz er.
Th e c o mp o sitio n is f o amed at 1 2 p p g ( 1 . 4 3 g/ c m3 ) . A
c o mp ressiv e strength o f 61 4 p si is ac h iev ed af ter 24 h o urs at
7 0 F, c o mp ared to a righ t- angl e c ement design ac c o rding
to th e p rio r art o f o nl y 3 50 p si.
EXAMPLE 1 0
Co mp ariso n in CRETE Sl urry
Th e f o rmul atio ns o f th e p resent inv entio n may al so c o m
p rise siZ ed p artic ul ates inc l uding sil ic a c o mp o unds, p o Z
Z o l ans and gl ass o r c eramic beads o f v ario us densities, suc h
as th o se desc ribed in c o - p ending US. ap p l ic atio n Ser. N o .
09/ 8 3 1 , 67 1 , Wh ic h is based o n Internatio nal Patent ap p l ic a
tio n WO 00/ 293 51 , and is h ereby inc o rp o rated by ref erenc e.
TWo sl urries Were p rep ared based o n a so l id bl end c o n
sisting ( by v o l ume) o f 3 9% Cl ass H c ement, h av ing a mean
siZ e o f abo ut 4 0 mic ro ns, 53 % h o l l o W sp h eres taken f ro m
c eno sp h eres h av ing an av erage siZ e o f 1 50 mic ro ns ( sp ec i? c
grav ity 0. 7 5) , and 8 % o f a mix ture o f Po rtl and mic ro - c ement
and sl ag h av ing a mean siZ e o f abo ut 3 mic ro ns mic ro
c ement. Th e sl urry f urth er c o mp rises a disp ersing agent and
an anti- f o am agent. To a ? rst sl urry p rep ared ac c o rding to
th e p rio r art, c al c ium c h l o ride is added at a c o nc entratio n o f
1 % by Weigh t o f c ement. To a sec o nd sl urry p rep ared
ac c o rding to th e p resent inv entio n, th e set admix ture B o f
Ex amp l e 1 is added at a c o nc entratio n o f 0. 2 gal l o n/ sk o f
c ement. Resul ts are sh o Wn in Tabl e 8 bel o W.
TABLE 8
Prio r art Inv entio n
D ensity ( p p g) 1 2. 4 1 2. 5
Rh eo l o gy Af ter mix ing
PV ( 0P) 99 1 00
TY ( l bf / l O O a2) 22 1 7
1 0
1 5
20
25
3 0
3 5
4 0
4 5
50
55
60
65
TABLE 8 - c o ntinued
Prio r art Inv entio n
Rh eo l o gy at 50 F.
PV ( 0P) 1 50 1 3 3
TY ( l bf / l O O a2) 23 25
Th ic kening Time at 50 F. and 1 500 p si ( h r: min) 4 : 58 4 : 25
Initial c o nsistenc y ( Bc ) 1 6 1 6
Transitio n Time 3 0- 1 00 Bc ( h r: min) 2: 4 1 3 : 00
UCA at 50 F. and 1 500 p si
Time 50 p si ( h r: min) 6: 27 6: 4 0
Time 500 p si ( h r: min) 1 2: 04 1 2: 3 4
Co mp ressiv e strength at 24 h rs ( p si) 1 54 6 1 1 61
Co mp ressiv e strength at 4 8 h rs ( p si) 2500 21 56
Vane rh eo meter test at 50 F. and 4 00 p si
Time to reac h 1 550 p si ( h r: min) 2: 00 1 : 3 0
Time f ro m 1 00 to 500 l bf / 1 00 f t2 ( min. ) 54 3 4
Th e f o rmul atio ns o f th e p resent inv entio n are c o mp atibl e
With th is typ e o f sl urry and gel strength dev el o p ment mea
sured at do Wnh o l e temp erature and under p ressure is
imp ro v ed, resul ting in sh o rter transitio n time f ro m 1 00 to
500 l bf / 1 00 f t2.
Wh at is c l aimed is:
1 . A meth o d f o r p rev enting Water ? o Ws during th e
c ementing o f a bo reh o l e Wh ic h p enetrates a subterranean
f o rmatio n Wh erein th e temp erature o f said f o rmatio n is in
th e range o f f ro m abo ut 4 0 F. to abo ut 7 5 F, said meth o d
c o mp rising f o rming a sl urry o f h ydraul ic c ement in Water,
p l ac ing said sl urry in said bo reh o l e adj ac ent said f o rmatio n
and p ermitting said sl urry to set in said bo reh o l e; and
Wh erein said sl urry is c o mp rised o f Water, h ydraul ic c ement,
a disp ersant, and a set- ac c el erating admix ture c o mp rising an
al kal i o r al kal ine earth metal nitrate and an al kal i o r al kal ine
earth metal nitrite, Wh erein th e sl urry gel strength transitio ns
f ro m 1 00 to 500 l bf / 1 00 f t2 in a time p erio d o f up to abo ut
90 minutes.
2. Th e meth o d o f c l aim 1 , Wh erein said set- ac c el erating
admix ture c o mp rises c al c ium nitrate and c al c ium nitrite sal ts
in a Weigh t ratio o f f ro m abo ut 1 : 3 to abo ut 3 : 1 .
3 . Th e meth o d o f c l aim 2, Wh erein said set- ac c el erating
admix ture c o mp rises c al c ium nitrate and c al c ium nitrite sal ts
in a Weigh t ratio o f abo ut 1 : 1 .
4 . Th e meth o d o f c l aim 1 , Wh erein said set- ac c el erating
admix ture f urth er c o mp rise gl yc o l s.
5. Th e meth o d o f c l aim 4 , Wh erein said gl yc o l s are C2 to
C6 al ip h atic di- o r tri- h ydric gl yc o l s.
6. Th e meth o d o f c l aim 5, Wh erein said gl yc o l is dieth
yl ene gl yc o l .
7 . Th e meth o d o f c l aim 1 , Wh erein said set- ac c el erating
admix ture f urth er c o mp rise al kano l amines.
8 . Th e meth o d o f c l aim 7 , Wh erein said al kano l amines are
sel ec ted f ro m th e gro up c o nsisting o f c o mp o unds h av ing th e
f o rmul a:
R1
Wh ere R1 and R2 are h ydro x yal kyl gro up s in C1 C4 , and R3
is a C1 C5 al kyl gro up s.
9. Th e meth o d o f c l aim 8 , Wh erein said al kano l amine is
sel ec ted f ro m th e gro up c o nsisting o f meth yl and eth yl
dieth ano l amine.
1 0. Th e meth o d o f c l aim 1 , Wh erein said set- ac c el erating
admix ture c o nsists o f c al c ium nitrate, c al c ium nitrite, dieth
US 6, 955, 220 B2
1 3
yl ene gl yc o l , meth yl dieth ano l amine and c al c ium bro mide in
a p ro p o rtio n o f 4 2: 4 2: 1 0z 3 1 3 by Weigh t in Water, With a so l id
c o ntent between 4 5 and 50%.
1 1 . Th e meth o d o f c l aim 1 , Wh erein said set- ac c el erating
admix ture is added to th e c ement c o mp o sitio n in an amo unt
th at p ro v ides a to tal sal t in th e range o f abo ut 3 to abo ut 20
g p er kg o f c ement.
1 2. Th e meth o d o f c l aim 1 0, Wh erein said set- ac c el erating
admix ture is added to th e c ement c o mp o sitio n at a c o nc en
tratio n o f abo ut 4 to abo ut 4 5 c m3 p er kg o f c ement.
1 3 . A meth o d f o r p rev enting Water ? o Ws during th e
c ementing o f a bo reh o l e Wh ic h p enetrates a subterranean
f o rmatio n Wh erein th e temp erature o f said f o rmatio n is in
th e range o f abo ut 4 0 F. to abo ut 7 5 F. , said meth o d
c o mp rising f o rming a sl uny o f h ydraul ic c ement in Water,
said sl urry h av ing inc reased gel strength dev el o p ment, a
reduc ed gel time and a density ranging betWeen 0. 9 and 3
g/ c m3 , p l ac ing said sl urry in said bo reh o l e adj ac ent said
f o rmatio n and p ermitting said sl urry to set in said bo reh o l e;
and Wh erein said sl urry is c o mp rised o f Water, h ydraul ic
c ement, a disp ersant, and a set- ac c el erating mix ture c o m
p rising an al kal i o r al kal ine earth metal nitrate and an al kal i
o r al kal ine earth metal nitrite, Wh erein said sl urry f urth er
c o mp rises at l east o ne additiv e sel ec ted f ro m th e gro up
c o nsisting o f ? uid l o ss c o ntro l additiv es, and gas migratio n
c o ntro l additiv es, Wh erein th e sl urry gel strength transitio ns
f ro m 1 00 to 500 l bf / 1 00 f t2 in a time p erio d o f up to abo ut
90 minutes.
1 0
1 5
25
1 4
1 4 . Th e meth o d o f c l aim 1 , Wh erein th e setting temp era
ture is in th e range 4 0 F. to 7 0 F.
1 5. Th e meth o d o f c l aim 1 3 , Wh erein said set- ac c el erating
admix ture c o nsists o f c al c ium nitrate, c al c ium nitrite, dieth
yl ene gl yc o l , meth yl dieth ano l amine and c al c ium bro mide in
a p ro p o rtio n o f 4 2: 4 2: 1 0z 3 1 3 by Weigh t in Water, With a so l id
c o ntent betWeen 4 5 and 50%.
1 6. Th e meth o d o f c l aim 1 5, Wh erein said set- ac c el erating
admix ture is added to th e c ement c o mp o sitio n at a c o nc en
tratio n o f abo ut 4 to abo ut 4 5 c m3 p er kg o f c ement.
1 7 . Th e meth o d o f c l aim 1 3 Wh erein said sl urry c o mp rises
a ? uid l o ss c o ntro l agent and a disp ersing agent.
1 8 . Th e meth o d o f c l aim 1 3 Wh erein said sl urry f urth er
c o mp rising siZ ed p artic ul ates.
1 9. A meth o d f o r p rev enting Water ? o Ws during th e
c ementing o f a bo reh o l e Wh ic h p enetrates a subterranean
f o rmatio n Wh erein th e temp erature o f said f o rmatio n is in
th e range o f f ro m abo ut 4 0 F. to abo ut 7 5 F. , said meth o d
c o mp rising f o rming a sl urry o f h ydraul ic c ement in Water,
p l ac ing said sl urry in said bo reh o l e adj ac ent said f o rmatio n
and p ermitting said sl urry to set in said bo reh o l e; and
Wh erein said sl urry is c o mp rised o f Water, h ydraul ic c ement,
a disp ersant, a set- ac c el erating admix ture c o mp rising an
al kal i o r al kal ine earth metal nitrate and an al kal i o r al kal ine
earth metal nitrite, and siZ ed p artic ul ates, Wh erein th e sl urry
gel strength transitio ns f ro m 1 00 to 500 l bf / 1 00 f t2 in a time
p erio d o f up to abo ut 90 minutes.
* * * * *