Note: Descriptions are shown in the official language in which they were submitted.
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ORGANIC REaOV~Y sysr~M AND ~l-~n
p~ n OF 1~ ~V~ON
The pl~cn~ h.-~,l.lion relates to a U~ A~I~ r~cu~ system and
meth-yl More ~ h~, the present ill~ ioll relates to a self~ ~ oil
AI~I r~o.~r ~l~q~ 1 and .n~lh~ of using same.
BA~KGROUND QF THE n~ ON
With the OCCU.lCllCG of oil tankers lW~ln~ ag.oull.l and sp;~li~ their
into wat~l..a~s, and with inland fuel spills u~ ~lA~ A~ ac ~ ~ and soils,
there has been a Qi~ifirAnt amu~t of acthity in the oil spill clean-up art. Various
,metho~l~ are known to ~ . oil once it is spilled in order to ple~_Ql dA~..agc to
aquatic life and of the e~ P~ Ch.~ irAl addili~_s~ porous ~ t~ iAl~;, as well asvarious sheets and bA~ have been ~ro~sed U.S. No. 5,120,598, Robes~n et al.
teArhes a mat ~r~luc~ se~l of polyvinyl Alr~hol ultra-fine fibers, which is br~
into contAr,t with an oil spill, so that the fibers absorb oil. The Robeson et al.
arrAnee~ rc.lui es rel~lu.dl from an oil slick once the fiber mate is sstul~atel. In
A~ iti~n, pre,, ~..Ably the oil must be rcl.lu.ed from the mat before the same can be
reused.
Nohmi et al.U.S. No. 4,229,297, t~r-hP,s a ~ lhod of s_~ala~il.g oil from
an oil Cl;)-~A;..il~g liquid. This lefere..cG teA(-h~s that the ll~ lure may be sep&~led into
tinrt phases by forcing the l~~iAIuç~ into conhct with the inside ~ ~ r~ (lumen) of
the llliClOpOÇ~u~ hydrophobic hollow fibers. (In this regard, the flow is ~f~,l~ to as
"down-bore"). This refers to the fact that the two phase ll~iAIUre iS forced do~m the
lumen of the fiber as op~sed to being passed into cont~c,t with the o~l~ide s~ ces
of the fiber, i.e. shell side feed. United Shtes No. 5,073,261, and Conradi et al. provides
a c~ re~'e c~n~ PJ having an inlet and an outlet and c~ ~sed of a water
el~/ious rubber ...~te ;~l The coll~rA~'e c~ il-er is cQI.~e.,ted to an inlet for
cllal~g an Q;l ..dlGr ~ hlle into the c~ er. The c~ el i~s con~l;~cd with
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baffles, etc., to ~n~ the oil therein, and the co~ ;nPr is towed to &nolher 10cAt;....
for oil fe~uu~
Coté et al., in U.S. Nû. 5,248,424, provides a rw lhPr v~. ;A~ n on hollow
fiber separalion technl)lo&y, and ~licrl~ses the use of hollow fibers for s- ~ara~ g v~uious
co~ e The fibers are es~e~l;Ally uusup~ltcd and are AicrD~Etl in ar~uatP-
rel~tinn~hir with one ~loL~l. This ~~ ee ~.~- .I would not be PJL~ e in, e.g. an oil
spill on a large body of water. Coté et al. make no ~ro.~ion for fiber ~ .P~
cllAngPs which occur when the fibers are in c~ntAct with, e.g. oil. In this C l..Ati~n, the
arrAn~.-.-P-.t would simply "bundle" or 'IcluLu~", inh~r~ ly 1e~1;n~ to erli~;en~
limitAti- n~
It is thus clear that the Coté et al. ~~ ge.nrllt is not adc.luatP for
sepal~lioll of an ol~iC liquid r~ se:l within an aqueous ".e~1;.--" The Coté et al.
ar1AI~ee~ ntiS~Q;~A11Y ~le~ ~e~ for solid particlllAte rc~o.~ from an aqueous ~AlulG
as û~osed to liquid-liquid se~ aliLll.
Taylor, U.S. No. 4,886,603, te-AchPs a S_~&laliûll m~th-xl where diesel oil
conl;1-..;.~AIed with water can be a~.p~e,.lly dewatered by ~---..l.;l~g the LUiAIUl~ thro.~
the lumen of LUiClopolous polyvinglidene fluoride (PVDF) hollow fiber m~nlPs
capable of sepalatil,g the oil as the ~GllneatG. The allA~ee-~ l employed is a tw~
stage llydro~hobic mi~ rop~l~ou~ hollow fiber m~llll~ which relies on forcing a two-phase
~lul~ down the lumen of the hollow fi~ers in order to a~alGnlly achieve sep~liol,
of the oil from the water. The Taylor l~f~ ICllCG requires the pa~ ~a~gÇ of a rclçl~-qtG into
a second chamber c.lui~ed with a l.~dro~hillic m~Lubl~lc in order to finqli7e the
.pl."r.nt and rcLuo.~ free phase water.
Ford, U.S. No. 4,846,976 te~ s that oil reLuûv~l from an oil-water
~IU1~ is best conducted if the LlliAIule is forced llllo~h the l~lnn~n~ Ford like Taylor
has inherent problems with ~l.nP~tG quality in terms of effiri~n~y of phase scl~dliu
without c~ )n.
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None of the above Citslti~n~ in~lirAte any ~h~irochP ..:-Al change in
rGccJ.e~Gd oil ~ LPs, other than dch~-llali~n.
Funk et al. U.S. 4,617,216, provides a ~cl~ e sG~aLol~ of
h~ ~ oc~~ s. In the disclosure, there is taught several dirrGlc,l~l ...P,Il~e for
pr~alation of a ~I~e"mbl~e for use on valious L~,~OC&I1~1LS. 'The disclosure does not
inrlir~te the use of hollow fi~ers having l.licluporGs and ful~lGr, does not specify the
adv~ntages of S~c;r;c directi~n~l feed for l,~aLng the h~o~l,ol~s
Breslau, U.S. No. 4,435,289, discloses a series of ultra~ll,aLon ~lOCGSS
and aypalalus with ~rG~u~ d ~r~rJ~ A~G. 'This l,~,f~rG~ce, is c~nr~ ..P~3 with ser~ala~
solllt~s, suspended matter or colloidal ~&~licl~s from a soh~ti~ n or ~ e;o1- byultrafill,atiol,. The Breslau feÇGrellce does not teach liquid-liquid Se~&latioll. This is due
to the fact that the system will not f ~i~ nl~ in an ef~rient ~--A~-ner as a liquid sG~aLon
a~ p~-dlus. In this ...~n,~er, the Breslau rerGrencG broadly relates to the Nohmi et al.
disclosure and would appear to be known to suffer from the same problems that the
Nohmi et al. ~ rhSure te~çh~.s.
There clearly exists a need in the art for a more a~ccd system which
is c~p~b'e of re~uovillg and r~co.e~ the o~ic l-~Ate.;~l from an aqueous system
which is erl;rient~ reliable and results in substantially complete sepa~alioll of the Ol'~ nic
phase from the liquid phase ~ ;ll,oul co..t~ ;o.- of one phase within the other. The
presPllt .n.~ llLon provides a snlutinn to this problem and sCl;-r;es the desirable result
of ~r~l.~ discrete and sub~tS~ lly pure phases.
SUMMARY OF THE lNVE~NTlON
One object of one e",l~l;~.len~ of the ple~rlll invention is to pro~ide an
u~d methrxl for oil recu.e r from an aqueous n~e~l;...n
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A further object of one e ..~ .P~t of the present invention is to
~ro~ide a methoA of se~ting an immiscible Ol~;al~iC c~...po~-~l from an aqueous
~iAIure col-la~ g the co,ll~und and an aqueous phase, c~ the steps of:
providing a plurality of hollow l~o~hobic fibers having ll~iCr~)~)lfS
therein and o~-se~l ends in~r~P~ le to the ~lu~c, the miclupor~s eYtpn~ling fromthe outside of each fiber to the hollow ;--lf~ r ~I~,reûf~
~i~s~u.ably forcing the ~ ulGlhrO~ the ll~icro~rf s under ~ .rr;~ =...t
pif~ ., to only permit p~Q~ge of the ;............. :~:ble olgal~ic COlll~ Ulld lLIO.JBh the
mi~,lopolfs and into the hollow i~.tc.l;ol, but ;~rr;~;r,~ for c~ll~se of the fibers and
p~csage of the aqueous phase;
collP-cting the immiscible Ol'~aniC col.,pound; and
discharging the aqueous phase ~ lly devoid of the immiscible
organic coll.pound.
The hollow fibers may be &llall~ d in an array, a di~el~ g ~At~ , a
parallel p~e..., iulel~c~,ting p~llelu, blln~llP~ into one or more bl~n~ Ps~ col~lated
into a mat sllu~ure or illCOlllOrated into a s~lit~1 le substrate, e.g. a cloth substrate or
a poi~lllelic ~elllbr~.e. Many further all~ge~l,el~ls will be readily &~)&rel~t to those
skilled in the art.
SllitA~lF polyolefin fibers which achieve the desirable results of the
~l~,se~ ntion are those fibers made by l~it~lb;~li Rayon such as the Stela~,ore~,
EHF and KPF as well as those fibers ~--~--ur~r,tllred by C~e1or-~e Co ~ulatiOll. Other
micloporou~ h~dro~hobic hollow fiber l.leml,l~nes may also be elll~Jl~_d.
It has been found that some types of fibers, when ~A~osel to oil, "swell"
or incur (li~"~ .Al GllA~S Use of a stA~bili~ine ...~ ~r for ~nAil~Ainil~p the fibers
in a spaced and connected relation s-~b. ~ ;Ally all.,~;at~s this ~La~.back and ple~c~
Wnlring or excess d~lullion of the fibers, particularlywhen the same are glo.-~cd in a
bundle. ~S litAb'~ .nAt." ;~lc for this p~ose may be ~ t~,r thread, Teflon thread or
any other ,..At~.,;Al which does not s~bsl~l~l;Ally swell in the presence of oil. A
c~;~e advantage with this ~io~Lsion can be realized in that if the bundle of fibers,
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mat, etc. is stS~hili7e~l with lC,S~ Ct to rl;~ DAlC1~AI~C,PS, the fibers are ...A~ ed in
a substantially regular spaced ...AI.nel ther~ror allowing the p~ ee of an oil or
C~ S~n~ A~ con~s ;t~ g feed stream to pass llle,~el~ r~ while c~ nt ctin~ a ~n~ n---.
number of fibers; this, of course, leads to a more erri~ system.
Co~ e.~nlly, the hrdr~hobic hollow fibers employed in the present
invention do not require any ~relleS ~ ~.t in order to achieve the results set forth
herein. This is in ~A~ Co~ 'tl with what has been ;--~ G-1 in the prior art and
sFerifirAlly the Coté et al. refelenc~, supra. In Coté et al. the h~dlophoWc fibers have
to be treated to render them hydrophillic, and accordi~ , it is clear that the Coté et
al. system has been ~le.;~-e~l for non-oil based s~a~atio,ls.
With re~ccl to fiber s~lrc!inn~ these same are prefe~ably ~ opvr~
with the average pore ~listmetPr of the pores typically in a range ~.~ g, for
,'~ 0.03 m,.rons (~m) to about 5 miclons (,um). The pore lliA.neter will, of
course, vary dPpe~ i~ on the intended use for the fibers and therefore may exceed
this range.
S lit~hle COll~ ~ Al ,..~le- ;Al for the hollo~v fibers can include, for
polyolefins such as polyethylene, polyyio~ylene~ polyl/lllene, polyis~.ll~le.K,
polyppntpne~ poly(~meth~lisopPI tPne) and their halogen-substituted deliv~ s having
at least one ~uolhle atom: poh~ ne and a halo~natfJ pol~ ,ne having at least
one flllorinP atom: copolymers of e~ el;'Ally .li~Q t~ ted lly~l~ s and/or
h~log~on-substituted el~lylf .~i-Any .~.~Q~t~dted ll~.ocall,ons having at least one fl-lorinp
atom, el~ A11Y ~ Qs~ (ated h~J1OC~bO11S and their hslnEPn s ~l,sl;l~led d~ rati~_S
including ethylene, propylene, butene, isobutylene, yelltelle~ h- ~f ..c,
mt-n~ fll1< roethylene, vinylidene _uoride, tlifluoroclh.~lellc~ teh~luor~th~l~nf~
trifluorochloroelh~lellc, hpy~fl~ ~lo~rylene and the like; and blend polymers such as
a c~ ml~;nAI;~ of polyethylene with polyyrop~l~nc~ polyv n~lidene fluoride,
polyt~ tr~lluoi~lene or pol~ nf, a c~mbil~Atiol~ of polyy.op~lene with
polyvinylidene fl~]oride or poly-teh~ or~lL~lcne and the like. F~fellc.l examples of
~-.~te,;~l~ employable inrl~de, as a main c~ t, po~ lene~ a h~ n~eA
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pol~_ll.ylene having at least one n-,c..; ~e atom, pol~ro~,~le,ie, a h~ .A~Gd
pol~pç~ylene havLng at least one n--~ e atom, or copolymers of two or three kinds
Of mr ~ ..e,s s~l-ctç~i from ell.~le.le, prc,~le,ie and tell~uu,o. lhrlene. It is noted that
where a plurality of cr~ -f~ having di~,e,ll critical ~ ~. r~ce te ~~-;o-.~ are c~ mhine~,
t_e more the plo~lliu,l of the c~ )-u~-t having a lower critical ~---f;~ce te-.-;~ , the
lower the critical s~rfAre te~ o.. of the entire polymer bec~...Ps Further, membranes
which do not themselves yield desired s~aralion ch~ cl~ l;rs may be ~I~;r;r"~ by,
e.g. vacuum d_~S;tio.~ to render them cArAl~le of the s~p~ation. This is inA;r~te~ in
the Nohmi et al. Patent ~l.r~ seA hPlelnabove.
In terms of a~al~lu~ for prS~iC;ng the present ill~enlion, an o,~anic
storage co~-lA;~Pr and ap~tus may be col~ t~ ~o~ eJ in any cGll~_llient
~nA~-~-Pr with the arrAn~e-~P-.~ of fi~ers suitably co~ Pcterl to the &l,~&l~ . The
apparatus may cn-..p ;ce a ~ litA~l~ pump cArAhl~ of ;..llur~ a pre~ure on the o"lc;~e
of the hollow fibers sllffiriP-nt in order to force oil lh_lclluou~h for deposit into the
storage cn~ .P,r without the cnllAps~ of the fiber.
Where it is desirable to have a self~~ i..e-l unit which is self-propelled,
the slor~ge cQI,~ Pr may ~colpo~ate a water discharge outlet which fu Ih. r may
inrl~ e a rolcibly I .h~ PJ water stream. The Ço~ ly e-h~ IPJ water stream may be
used to propel the rlo~l;ug re~ o~ system th-o.Jgl4 for ~ rl~ an oil slick.
The &p~&lalus may S ~ A11Y ;~ -de a rcce;~- such that the a~&laluO
is re.uolely controlled. This may include a radio rece;~ l or other cl~l.~...agretic
means for (letectine a remote signal. The &~A atu~ may also be mAnuAlly moved byany s-lit~hl~ means, and may ;..rlu(le ~-~I~e~l;Qn rLslures to permit towing. The use of
re-l.ote controls l,e~ a user access to an oil, c~ Al or other co--~ ,A~l spill
area even where there are ha~dous cn-~lil;nm, e.g. surface fires, toxic fumes, etc.
Land-based ~ el..s for inrlllC~~Al uses and acquifer fuel spill r~-"e~ . are also
useful.
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A further object of one P~ n~P~l of the present il.._nlio.l is to
.o.;de a ... ~ ~ of s_~&laling an ;.. ;-o;~k Org ~iC co~ ouild from an aqueous~iJ~IUlG C~ e the CO1111)0~d and an aqueous phase, cr l~.pl;c;.~g the steps of:
pr~ g a plurality of hollow l~dlophol~ic fibers having micropores
therein and o~l,osed ends i1 ~cc~c~le to the ll~AluiG~ the m~,lOl)Or~.S v-lf n~ e from
the outside of each fiber to the hollow ;~-lc~ r thereof;
,a~ g a ~r~,~urG diavrGnlial l~h._Pn the ~lur~ and the hollow fibers
such that the m~lulG is under higher ~rvs;~ulG l~vlaL~v to the fibers, the lJrG~uiG beinB
s~r~ 5c ~t to permit passage of the o~anic co.-~po~ but in~lffiri~nt to allow the
aqueous phase p~Qcage into the ll~ClO~ ,S and for the hollow fi~ers to collapse;c~ nt~ctirle the ll icropolvS of the fibers with the ~IU1GS;
cr-llectine the immiscible org~ic colllpoulld, and
disch&lging the aqueous phase sub~ nl;~lly devoid of the immiscible
orgallic compound.
The ~rGSent invention also has the advantage that a host of
phyc;cochf .nirAl ~ro~Gllies can be altered for oil. Examples of the ~lo~llie,s that are
r-hA~ge~1 inrll]de one or more of liquid v,sco;,il~, density, pAIlicle size, API rating, pour
point tGmp~ iCtill~Si~n char~ t~ s and COml~l;On ~rr; i~ -.~ char~cle~ ;rs
inter alia. By providing v~.;Anr~ in these ~ro~Gllies, a more co..~ r.;ally desirable
product results and inherently adds value and gr~ atGr utility to the tleatPd ~r~lu~,ts.
A still further object of one eml~l;-..P-nt of the ~r~ SPllt ill~ntiu~l is to
provide a .. ~1~1 of s-ltering the phy~;~hf .n;~Al pro~.ties of crude oil, the l)ro~,lies
inr.lu~ at least one of liquid viscosity, density, ~licle size, API rating, pour point,
flictill~tinnchar~l t~ ,andcoml~liûller~ n~char~ct~ ,cO ~ l.c;~.gthesteps
of:
providing a feed c~ ,.l;.i.l;.~ crude oil;
~ r(n~;dillg a pol~,me.ic matrix having pores tLerellu~ougll for selccli.eh~
p~ the crude oil;
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fo ..~ing a p.es; u~ GlGlllial across the matrix such that the ~leS;~UlG
is ~ .rl;~ P~t to permit passage of the oil throu~ the llli~;ro~rGs, but ;n~ ient for
cQll~pse of the matrix; and
collecting the oil, the oil having at least one altered ph~ ..;r~l
pro~l ~.
The ~rGs_l~l techn~l~D also has utility in the fragrance il,du~ . To this
end, the methnfl may be employed to dewater essential oils.
It will be &~lGc;31eA by those sl~lled in the art that allllo.gll there is
s;o ~ of the use of the a,~ t for leCO~,.in~ oil, many immiscible o.ga,~ic
s~bsl3~ s either mixed with or no~t;.¢ on a water body may be lecu.ered using the
COl~C~pt in the ~iese~ ol~.
The appalalus d~ ed herein has nulllelou~ le uses. In afl~litinn to
self~ 3inP~ or ~olatioll &ll~ge ..P~tc using partially land-based e~ ip-..P~.~, the
prwenl e~llion may be employed in a towing all;3ne~...P-~t where the hollow fibers
are towed behind a large floating vessel, e.g. a barge or other flo~tine carrier vessel.
This has the tli~tinrt advantage of removing a s~ A~ l rei.i lue as it is discl~alged
from the vessel. In this .n~ . r, the all~ef ,..P-.I el~ ly "self-cleans" the surf~~e of
the water.
Other alrS~I~er~nP~ include the use of the fibers for the ~u~se of
t~ealillg a conl;....;l~teA pond. The ~l~.~g"n.Pnt may also be totally subm~l~ed in a
c~ .ni~lp~d water body to assist in cle~l~;u~~~ for ~ -- n.l,le a ~..1 ...;n~teA river
se~iment bed, lake bed, etc.
The fibers, when used in a mat al~ ge ..Pnt or bundle all~n~en.- ~~t may
be pos;tinned in an area to be treated in a sta~ Ug~ .l of bundles of the
fibers, mat arr~nge-..- ~-ls, or woven or non-woven mat afr;u~ge-..P--~c or empl~ying
subsllates for the ~u~posP~ of :~up~ ing the fibers, or any c4--.bil~ of the above
arr~ c
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Another advantage of the ~ll~GnliO~IiS in le,.-uv,ll~ an or~,nic mAtçriAl
from a~uiÇtl~, soils, etc. coulAini~g the O~ c~lAle~ ;A1~ and water, for ~. , 'e, from
c~ Ated ac ~ . Through the above methodol~Gy, it is possible to utilize a
m~llllP cQI~A;l.;ng the hollow fibers to r~,.,o-_ the or~-ic from the water, while
leaving the water in situ. This ~.;ales the need to treat the water accor~ling to
govt;~ lenl or other ~ -ds. By using the above .n- t1-~ok~y the hAn-lling
re~luilen~ for the water can be completely avoided, res-llti~ in time savings and
other llullle~fous advantages. In ~Acldih~n e ~li._ly re~lluving the or~,l)ic lnate.ial, the
meth-)dnlogy also f~ t~A~tes parhClllAte filtration.
Use of the fibers and a~ ~ ..Pnlc herein can be employed in
cn.-.~ AI;~ with ~ lA~ A~t booms or in c(~ A~ with any other cQ-~IA~ Al~l
clean-up ~lel,.s. To this end, the outside surface of the hollow fibers in cm-~-e~l;~.-
with a source of posilive ~e..;~ure can be ~o= IT~ ed l~eh ~l. con~e~ -.A1 o~-ophilic
mats which act to attract the oil thus ~nhAI~ g the extraction ~ rr;- iel~cr ~f the oil from
the water body. This would be cl~cti~e in certain 5;lUAI;~ .C and the hollow fiber array
would be useful to draw the oil out of the mat ~ _nling salul~lion of the mats with
oil.
In prncti~in~ the above method~loey it was disco. red that if a
h~ phû~ i- matrix having pores l~.ere~. ou~ were employed in a ~re~ e di~erenlilestAbliQlled from the fee~l~;de of the matrix to the outlet side, that a crude oil s---. 'e
underwent ~;W.;ri~ l chAnge~ in some ~h~ l and C1~ A1 pro~llies.
The positive change in ~re~sul~ may be g~ne,~t~d by ~...~ l of the
higher ~reSi~ulc by liquid head p~e~;~Ule., ~h~ g, gravity, or e~ the
all~.~c. ~..ent within a shell or tank to provide for the ~,e~ule.
A further ~nl-;sil;O~ if one desires to exceed the delta P across the fibers
such that there would be water breaklhrougl., could be carried out and the entire
breahll~-~ou~ ~IlAt- ~;AI~ i.e. o,g~ic and water, could be then separated by observing the
delta P to exclude water breakll.r~,ugl, in a later step. Thus any cr)n~ Al~ l of ~ g
CA 02248280 1998-07-08
teC11nrIO~Y lQge!he1 with the ~-.P!h~ of this in.vnliGll may be cQmhine~l to effect a
certain result.
Having thus generaLly described the i,l~_~.lion~ le~.e.lCC will now be
made to the ~c~l~ ..pA~ dr ~ la~ g, prefe~le.l e
BRI~ D13Sa~lON OF THE DRAWINGS
Figure lA is a glilphi~l representAhnn of the ~r~ .~lag~- of oil lemO.Cd
from a sample as a r -~ of moclnle length for a given pre~ure for down-bore feedo~lalion for 50/50 and 94/6 volume ~r~,t water/kerosene miAIul~, illu..ll~ti~g adccleasc in rell,ovdl erli~,e~.~ at about 95% to about 50%;
Figure lB depicts similar il~ro~ n as in Figure lA, but for shell side
operation i~u~Lla~g 100% (Olgal~iC) ~rOSellC re~lov~;
Figure 2 depicts ~ OSene reco.e.~ rates as a r~~ of the ~rcenl
kerose.le down bore feed ill~,sL aL llg an as~ Lolic curve;
Figure 3 is a top plan view of a mat acconlil,g to a pn,rc.l~,d
embo l;",P."I;
Figure 4 is a cross-sectlc)n~l view of the mat in Figure 3;
Figure S is an enlarged view of a fiber used in the ~lcsel,l in~cnlion;
Figure 6 shows a magrlifie~ view of fiber in illu~Llali-lg a first ~-,ro~r~
morphology;
Figure 7 shows a magllified view of the fiber illu~Lr~ling a second
'JpulOu~ morphrlr~,
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Figure 8 is a croo-o socl;n~ Al view of a ful lhGt em
Figure 9A is a yt;~D~cclive -view of a still further ~.m~ ...e~
Figure 9B is an enlarged view of a polliol~ of the e..~ in
Figure 9A;
Figure 9C is a top plan view of a system ~lu~ , a mat of Figure 9A;
Figure 9D is a side ele.ationAl view of the embo~limP.nt shown in
Figure 9C;
Figure 10 is another eml~;-llPl-t of the yl~sGn~ vl~tion,
Figure 11 is an All~ - nAte Çmlx)~ of the present hl~,nlion;
Figure 12 is a x-l.f~.-AI;s illuDll~lioll of a nGh.ol~ of mn~lllP~;
Figure 13 is a ~ se ~~Al;n~ of particle count as a r-~-~ l;n~ of y~licle
size for a crude oil sample co,l.~ -Ally deh~Jldte.l,
Figure 14 is a r~pi~s~ ;nn of a p~llicle count as a fu~ l;nl~ of y&~ le
size for the sa_e s~mrle as in Figure 13 but for a treated ~mrle,
Figure 15 is a ~/iscoDil~ tGl.lp~,lalun, chart illusl,aling l~ ;s ~iscosiq
as a f~ l;n-- of tGm~ for a further ~ of a COll.~ .nAlly dch~alcd
crude oil .~-.ple;
Figure 16 is a ~ph 1 r~pr~ l;o~ of ASTM ~ till~tinn data
il.rlicAt;.~g t~ y~lulG as a ~lnctir n of rlaclio~ tilled for V~iouD fractions in the oil
sample of Figure 15 after coll~ Al deh~tiol~,
CA 02248280 1998-07-08
Figure 17 is a represe~ . of a ~liele count for the oil sr_ ple of
Figures 15 and 16 as a r~ ;n~- of ~licle size after co-.~e~ -Al dch~lrdlion;
Figure 18 is a ~isco~ telu~rdlllre chart iilU~ll'dtil~g ~ P~A~;~ viscosity
as a ~mr,tinn of te~ dlul~, for the oil sample set forth with r~t to ri~ ,s 15
thlou~ 17 subsequent to t1~A~n~F ~t accol~il.p to the present ih~_llliOl.,
Figure 19 is a ~l-hi~Al represe ~ ;nn of ASTM distillation data
in~ e tvlu~lalur~ as a ~lnch-~n of fraction ~ tillecl or fractions in the oil sample
of ri~ res 15 through 18 ~ubsc~luellt to tl'e~'..PI~t with the lJ;esPlll invention;
Figure 20 is a representAti~n of a palli-,le count for the oil sample of
Figures 15 through 19 as a r~ - of ~liclc size sub~quellt to lle~ -l according
to the present in~elllioll;
Figure 21 is a visco~ tel.lpelalule chart illu~ ing L;-.~.n.AI;r, viscosity
as a r.-,-c~ i-... of te~ ure for yet A.~ hFr oil sample after CGll~v~ onAl del.~dliol~;
Figure 22 is a ~.hi~ represent-oti~n of ASTM ~liQdll-otion data
in~lir~ p, t_,l~ lalUlc as a r---c~ of fraction ~lietille~l for v~ious fractions of the
s-omple of Figure 21 after coll~ ;.. .Al de}~dlation;
Figure 23 is a l~p~S~~ ~I;~ of a ~ahlicle count for the oil ~o . le of
Figures 21 and ~ as a r,-", l;- " of ~licle size after con~ 1 dch~dlation;
Figure 24 is a viscosity tel..~alure chart illU~Ilatillg ~ P-~AliC viscosity
as a r~-"c~i- ,- of telll~l~lule for the same oil sample of Fi~;ule,s 21 ll.lougl. 23
subsequent to lle~t~F~t in accordal~ce with the ~le3e~nl ill-e~lltiUn;
Figure 25 a ~~ l r_p~ se~lAI i~ .~ of ASTM ~ tillAti~n data i~ ti~g
telupelalure as a r ~-ct;~ ~- of fracdon ~licplle~l for ~alio~s fractions of the oil 5P li~ of
Figures 21 throu~ 24 su~se~u~ntto ~ with the ~lcs_n~ _.lliol.,
CA 02248280 1998-07-08
Figure 26 is a represe~ of a p&~lick count for the oil sample of
rigules 21 through 25 as a r~ n of ~ licle size subsequent to l~ ~n~ t aCCOldil~g
to the present i l.~nlion;
DETAIL~D DESCRlmON OF THE PREPeRR~ E~MBODIMI~N15
It has been found that ..~A.;n...n. oil-water sep~t.Lon rates may be
~re~ te-l using Poiseuille's formnl~ This form~ is an ~ ~ession for the volume of
liquid per second (V) which flows lhlou~h- a c~p~ ry tube of length L having a radius
R, under a ple~ e P, the ~cosil~ of the liquid being t1. P and V are d.le~
proportional, i.e. P - KV where K is fLxed for a tube given co-.~ -t length, radius and
liquid viscosity. This puts an ~bsolute upper limit on flow rate per fibre or m~lllle
before H20 breakthrough ~r~ PO,O is r~~-lleA By ~ul.~h~ 6 the feeLl~ l. to
be sepal~led to the outside of the fibers, the pl ~ Ul~, drop across the m~1le is much
lower, thus, the phases can be readily isolated at much higher water and oil total
feedjlleam rates, which is a ~lictinrt advantage over the prior art.
The Figure lA and 2 graphs show the inherent 1;...;lA~ of prior art as
se~l in r-~.--l,le lQ As illu~ ted, the &lllOUllt of orgal~ic~ e.g. kerosene, present
in the Qqmr'r cannot be entirely re,l-o.ed from a sample cn~ y a ~lule of
organic in an aqueous ,..eli-~-n This is ;..~ led by the ~ll-plote which is slightly
above zero and i~ Ates that regardless of the ~re~su.e or length of the fiber orm~llle, 100% pure phase oil re,..o~l in one step from the aqueous phase is
impractical using the prior art.
In col.h~l, Figure lB shows the ~r~-~age of oil re~uu.ed from a
sv , '- as a rU~ ;n~ of m~-ll~ length for the same feed rate as in Figure LA. It is
clear that 100% oil removal, with the present i~ nho~ is achievable lr~ h~lu~-l;n~
of a sample on the shell side of the fibers. With the present in~enhun, this ~j~ifi~nt
advance in O~ u~iC lec(~.e~ is achievable.
CA 02248280 1998-07-08
The ~uçr~sc of the m.f nlioll is believed to be the result of a CQ. . ~ AI ;-.- .
of factors, i--..l.,.lil~g the use of fluid ~l~ics as applied to multi-phase flow; the
erl;~;e~ r of the polyolefin L~ U~Ol'~U,i> hollow fibers; the effect of v~uious
ph~ oc~ Al ~iOp~l lies of oil versus, for example, water on LUi~o~lUuS
poly~ ini~ fibers; the ~resence of a ~o~ piesi>ul~ ~--rl;r:P..-l to force the O1~5~niC
...~tf-;~l from the aqueous L~lulf into the mic,upoles and subse4u~ into the
lumen, but ;., ~.rl;-;e..ll~ strong to force the water through the Lui~r~l)ol~s unless
uil~ d as part of a larger ~rocf ss scl-~ ~..e and other similar fPctor~
Figures 3, 4 and 5, show an ap~ lus of a first çm~ l of the
~rcselll i,.~e,ltioll. The mat, num~ll 10 (Figure 3), c~mrrises a plurality of individual
hollow fibers 12, e.g. h~dro~hol)ic having a hollow intPri-)r or lumen 13. The fibers 12
further in.-lllcle a plurality of spaced apart parallel Luiclu~res 14 (shown in enlarged
detail in Figures 6 and 7) ,Yt~n-ling from the outside of the fiber to the i.~lf.. ;o~ of the
fiber 12 such that the miclo~ores are in CQ~ t;n~ with the lumen 13. Generally,
the pore sizes of the ~u~o~rf s 14 will vary ~1.-,~h..,.l;~g upon the fiber ...~lf - ;~1 As an
~e, the pore sizes can range from 0.03 Luicrons (,um) to about S Luicrons (,um).Broadly, the mic,o~ores will be large enough to permit ccept~ flux, but small
enough to exclude water due to sll~fAGe tel~sion effects of the h~û~hob;c fiber.
The fibers may have an internAl ~ ,..eter from about 0.001 cm to about
S cm, yr~l'ably about 0.005 cm to about 1 cm and most desirably about 0.01 cm to 0.1
tcl~ (cm) in the case of poly~ lenc fibers.
Preferably the fi~ers ~ -r;ce a L~uphobic ".Ate. ;Al illu~llated
les of which may inrlude polyolefins such as: po]!JGlh.~l~ne, po~ ""l ne,
polyl,.lle,le, pol~ol).-lylene, polyl~ ntene, poly(~melll~l~o~ ene) and their halogen-
substituted de~i-ati~es having at least one n--O~ e atom; ~ le~le and a hAln~ ~-AtGd
pol~sl~ ne having at least one n~lol;~r atom; copolymers of ~ ILYIe.~;~A11Y ~ t~-.at~d
hydroc~bû,lsand/orhAlngon s.,b~ ledethyl~ Ally,.n~ .aledll~oc&ll,onshaving
at least one ll~lo~ r, atom, ethyl~ n;~Ally ~n~lv~ ated h~ IS and their halogen-
s~ll)slil~lle-l deliv~ti~l~s ;..~I.IAi~g e~ lene~ ,~"o~ e, butene, is~.ltyl.ne, ~ e,
CA 02248280 1998-07-08
hPYPn~ n~ e~ v~ rlid~.~e flllorid~P, hi~u~ro~ ne~ t~ ~luu.~~
trifluoroclor~ll~ ,ne, hPY~flul~r~ro~lelle and the like; and blend polymers such as
a c~m~ t;o~- of polyethylene with pol~lo~lene, poly ~,~ Ldelle fluoride,
polytt;h~uoi~tllrlene or pol~ ene, a coml).-.~;-... of pol~ro~lene ~nth poly
vinylidene flnr)nde or polylet~ oloe~ylene and the like. ~felle~ examples of
Il~A~e. ;AlC employable, as a main ~ ~ P ~ oh~etll~lene, a h~ln~ ~AIed ~l~ell.~lene
having at least one ll.~o e atom, pol/~,rop~lGne, a halogellated pol~pro~lene having
at least one nu~ atom; or Cû~O~y~uPl~ of two or three kinds of mrnomprs s~lectP~1
from ethylene, ~lo~lellc and tet~ olo~ ne.
As a further option, the lllGln~lanGS may be o~ionally ani~ ulJic with
l~;SpC(,t to inside pore ~h~lclulc versus outside pore structure, morF~ol-d, pOlosi1~J~
P.mirAl cGm~ n, inter alia. Sc~l;o~- of this ~r~el l~ will depend on the ;-~tc,.~-k;~
use of the fiber.
In a ~rl fell~d G-.~ -.t each of the fibers 12 i.~cl.Jd~s open ends 16
and 18 (as illush~led in Figure 4) for the emk~im~t n~ g on s~ e S. In this
embodimP-nt, ends 16 and 18 are in CQ.."~ if).. with rec~ ~tacles or c~ 29.The ends 16 and 18 are ~..Ai~lAir~d such that the ends are within the co..~A;-~er and not
in con~Act with the fluid, to be hGatGd. This may be achi. ~_d by potted seal 32 as
shown in Figure 8. Valved ~ch~ge ports 30 and 180 are provided.
Cl-n-11lit 26 l~le~l,s positive~p,es~ure pump 28, which serves as one
form of illllûduci~ ~res~ule into sealed cn.~l~;..,r 29 and thus the fibers 12.
In use the C~ Ain~ 29 are sealed and the ~ S;~Ule effect created by pump 28 is
~A~)el ;~.n~d by each of the fibers 12 of which the mat structure is made ~'nndUit 27
draws the organic/aqueous miAlure in for ~ e u ;-rd illl~uJu~ into cont~t with
fibers 12.
In o~.alio,l, when mat 10 is ~ ed vithin a water body for the
~L~pOSG of r~movmg one or several C~nl~ -L~ the ~silivc ~re~ule pump ~ is
alilu~ed which draw the feed. As the fibers are in CC'~ A~ with the
.
CA 02248280 1998-07-08
c~ A~Il;nA~t e.g. oil to be removed, the oil is forced via c~ u~i,-Pl~ 29 into cnntr-t with
fibers 12 via ~ u~les 14 and is ~ .,lually c~llPctetl The density of the a~ ..Pl~t
10 will be s~lected to float in the ~ I.lA."i.nAnt to be c~llP,ctG~l in order that ...A~; Il...n
possible surface c~ntArt of the individual fibers with the c~ J~.n;..~l is achi~ l. The
lr~atcd water e-ffl~lent is dischal~d lLlou~l- port 30 and the Cr~ A~ Al~ iS disl l~arged
through ports 180, or stored in rece~ cles 20 and ~.
Figure 8 shows a further AltGl~nAtG em~ ~ Access to the fibers is
achieved by providing a side port feed inlet 31C for l1AU~ ;Ug a u~iAlule of theorganic and the aqueous phase and discharge port 31D for dischalgil~g the aqueous
phase. The cnllected Olgon~CiS diSClll ~ d ~ O ~ 1 ends 16 and 18 and ~ollPcte~ in
recc~lacles. The o.~dnic ...Atel ;~l cnllPcted via the fibers can be dischal~d (not shown)
by any sl~itAhle means. Seals 32 keep the fed and collected Ol~;al)lC I~Ale~ ;Al sep~led.
rigules 9A, 9B, 9C and 9D illu~ te ful lh~ e~ of the present
iu~elllio~. Figure 9A, shows a pCl~ view of a fi~er mat mo~lllle, ;I~ Ated by
nulllel~l 40. The ends of hollow fibers in the mat alli...ge...Fl.l are fnicedly sealed by a
tube sheet or l.olling colllpûund to each of the lece~dcles 20 and 22, the diop~itiull
of the individual fi~ers of mat 40 and the rel~tion~llir with 20 being shown in Figure
9B. The oil is c~llected in reselvo.l~ 20 and 22 as i.l-li~t~ by oil 42. This m ~lnle
rc,- ~nAticm is ideally suited in use, for ~ F, a pl~ c~ l c~ er 46 such as thatshown in Figure 9D. The feed would be introduced into the col-lAinel by, e.g. a pump
48. The mats 40 could be set up in a vertically spaced apart ...A~ner as ;~ AteC1 in
Figure 9D and rulll,~l, as Figure 9C illui llates ju~ l~sed ~l~uge~n~ c of mats of 40
could also be employed. Cnllecte~3 oil within reservoirs 20 and ~ could be removed by
any s~litAble means.
Figure 10 shows a sc~ -..A~ ;C view of a ful lhcl c-.~l~li-l.- n~ ~ here~ the
~ .n. nl may inrh~le a nozzle 66 ".~ inwardly and in c~"--"~n;rAtir~, with
vessel 56. Vessel 56 inch es an inlet 67 for extractant Ol~ iC recycle, make-up, or
Ievel control. Also, inlet 67 p~, ~--;L~ access to vessel 56 such that the c~ ;o~- of
layer 70 may be sdccli~cly altered. The noz:~e, in use inlr~luces a
CA 02248280 1998-07-08
~n~ A.thb~ter/~tal composition into vessel 56 for se~alio~ The result is
generally that the .~ te.jAle stratify into layers 70,72 and 74. Layer 70 generally CQ~'Pi -
~the Or~,alllC phase, layer 72 COI~ lQ a ~lu~ of phases (water, coAl~4-.~s, etc.) and
layer 74 essentially comr~i_es water. It is known in the art that where the olg&nic~,
CO.I~An~ , etc. have a ~at~. density than water, the order of the ~llt t~fi.~AIi~-n will
vary in accoid~ce with the di~erence in density.
Outlet 76 on vessel 56 d;~ lja~ -t the mat 10 yro.ides the
extraction of the Ol'~iC layer toC !1-,r with metal COm~uLuldS. Outlet 78 p~u.;~es for
the discharge of S~ SI~ ;A11Y pure water devoid of the metal cl~rlG-.I coor-l:- At~3
c~",p~""~e or or~a~ics.
As will be al,~rer;~tG~ lo.~iOi~ may be made in system design and/or
opelation for a IIL~t ~ nL~/phase o~vlatioll for ~;-nnl~A..rous sequential or scle. L.e
removal (e.g. for enl~ n~l.l) of de ired c~n-p. ~P ~L~ from vessel 56. The a~alus
of Figure 10 may ~ ;.vly be useful for illclvas.l~ extraction of ultra fine oil
droplets from water by ~ n;-~linn~ of the etn~ ;on, ~--c;ng co~les~nr~ with andlor
extraction of oil into olga~ic layer 70.
Figure 11 shows a fuu~el e.~h~;n~ l of a solvent v..haclion system.
The a~ inrlllclPs a cq~ vessel, d~noted by nUlll~lal 80. As shown, the
system incll]~lp~s a first mat allA-~ P ~l 82 u~ nl~s&d of fibers 12, which C~ - Ale
at their tf.~ l ends with a first extractant reservoir 84, adapted to carry à suitable
extractant, which may either be forced lhrou~h the fibers or diffuse naturally. Where
the extractant is to be forced tlJlûu~ the fibers 12, a suitable yO~ v prvs~ure pump
84A or other s~lit~ble means will be employed and CQ .ne.,te.l to line 84B. The second
rGscl~oi~ 86 may be v.uplo~_d to inrlude similar clP...,..~ 86A and 86B.
As dispovl~ed extractant flows ll~u~ the body to be tr~,ated as jn~ AtP~r1
by arrow A in Figure 11, the extract may be reco._led by the Upp~ lOSt mat
arr~npe... l~ 82A and ccllected in res~ oi~ 20 and 22, the l~tlolll mat ~l~ ,&.,l
82 may be substituted with any s~liS~bl~ means for ~ 8 an extractant, etc. into the
CA 02248280 1998-07-08
body of mAteriAl to be treated. ~ples ;~ de simple ~lr~r~ted tubes or nozzle
~lA.~E~ u IllPr still, there may be employed an P-lf"~Al source of the
extractant, etc. which is deli~ered to the mat all~ e-..P~l 82.
In an A~ A~;~e em~,~ n~ the vessel 80 may include a pump 88 for
pl~ gvessel 80, providing the ..ec~CG.I~ ~es~ulc difrcre~ across the fi~ers 12
to effect the se~&lalioll result.
By providing an outlet 76 and further in view of the fact that the mat
~ gP ..P-..t 82 composed of the fibers pe-...;~ le,l,u~ral of or~lic c~ c _s
well as various m-otAl~, the ~ l~n clearly has utility in the mining art since the
gf -.- -.l can provide for reco.eled metal values ~-/hich would otherwise be lost or
ble.
It will be readily appre~:~te~l by those sl~lled in the art that the present
invention is clearly applirAblr to removing soluble c ~ lAl~lc from a water bodyC~ in;-~g CQ.~ AI~I~; dissolved therein. It is cleark~ within the purview of the present
ill~t;lllion to apply s-litAhle 11e~ P~ ~pie~:~tP~d by those skilled in the art~ for the
~ulpose of ~rC~ an aqueous phase from A~-ot~-Pr phase. In this .~ , once
the mixed phases are fcrme~l, the fiber mat or bundle all~l~g~-..P-l-t or fiber array
accoldi"g to the present i,.~enliol. may be employed for the pulpose of ~al~ti~lg, one
phase from the other.
Where the conlAn~ Al~t comprises any oth~r h~dloc&ll10n nO~t;~c on the
surf~c~ water body from, e.g., an oil tanker spill, one or several of the mats may be
employed for reco.elil~ the oil from the s~ r~
Where telll~l~tule i,lcleases the ~iscûsil~ of the oil or the COl~ t
is of a highly ~cous nature, the viscous co~ .;n~nl may be diluted with a s-lit~'e
ent~ e.g. a liquid l,~o~l,on, or any other 9'utP~F viscosity .n~;l';.~.r. Further, the
~~i5cùus c~ A~ninAI~t may be heated to reduce its viscosity, if practical. In this n.~l~ner~
units CQ~ p the IlliClupufO.lS hollow fibers can readily f...l~l;n1~ in a variety of
CA 02248280 1998-07-08
Cll~ L'' As ~ JC'~od the mqteriAl to be treated f~.~Ai~Q metAl~s~ a s~it9~'~
ll_~ l f~ .f .t regime may be employed to add a ~ hPlqnt or other Coll.~ ;onAl additive,
or to cool&ate the metal ~.At~";Ale and render them solu~l~ in the Ol~ lC phase and
in the instance where the ~..AIc - ;Al in~ fles insoluble ~&~ vl~lcs, e.g. sand, it will be
readily undel~lood that the ~lell~A~ regime may inrlu~e filtering, c~ ;r~ g~
c~ qnt jq"f~flitif n or other f 1~ 'A1 llGAI~-P-~ GC~ B, cooling, or any ~ AIi~ of
these. The ylCIl~A~ - .t regime will de~ .~1 on the nature of the ~Ate~ ;Al to be lleatGd
according to the ~ odoloeyofthe ~lesenlil~ nlion. In &~ ;o.~ewherewater-free
fuel or oil is critical (such as that required in the air,l~l industry or in em~ ,e
g~nGra~ols), a l,lovisiol. is made for the use of any variety of the known dch~d,alioll
techniques as adjuncts to the i~ ,lllio~ amples of s~l;tA~c teC-l.~ ues ;~ re gravity
tr~l,pll~g, absolption, etc.
l;-- es oil-water rn~ces may r~-luilc ~ , prior to c~n~t with the
fibers. As oil cools the s~ lub-~ity of water in it may dc~ and water droplets may
form. Au~dliary dehydration can Çl;~ Atp~ this.
Figure 12 sc-l.~ I.AI;rAlly illu~llatcs a neh Ol~ of m~llles as for . r'e
of the type illu. ll~t_d in Figure 8. The ~verall llch Ol~ 134 inrhl-les a master
feedsllG~ inlet 136 for reGAi~e oiUwater into n~h olh 134 for lre~l~..Pf~ therein. The
lwolL inclu(les an oil d~schargG outlet 138 and a water outlet 140. Optionally, any
number of individual m~lyles 120 can be c~ e~ileA in sequence to Acc~ te a
specific ay~al~tus rG-luil~,~ent. As a further All~J..At;vc, outlet 140 may yrovidp a
re~;lillg loop for ~e.mllo-.lu(~ e S~bSIAI~I;A11Y O1~ 1I1C free water into inlet 136.
Finally, with r ,s~cl to the choice of ~..At~'.. ;Al of which the fibers and/or
bundles may be con.posed, it will be ap~.~ec:~te~l that the fiber ~l~S ~ will depend
upon the ~pe of cn~ Al-~ to be collecte~l In this ~ cr, the fiber ...At~J ;Al will be
selecte~l such that the co~ does not dclelcliu~ly alter the yrop~ es of the
fiber with lG*~CCl to lumen size, internAl ~liam~l~,r, C~le~A1 fliA-~-et~r~ pore size or
s~l~fAce charAct~ l;cs such as h~nlço~hobicity of the fiber and/or pore.
CA 02248280 1998-07-08
It will be ~ loocl by those skilled in the art that the ~rOCG~S of the
invention can be cnmhin~fl with con.v~ n~l procGsses.
Having thus ~ ~1 the ill.vn~,4 rvfGrG~lcG will now be made to
. les which set forth the data g~vn~l~tcd as a result of the use of the meth~ology
set forth herein.
For Examples 1 th~ough 5, and 7, 9 and 10, the app&~alus that was
employed for the testing is generally illuDl~Gd in Figure 8. The fibers employed were
EHF 270W, EHF 270FA or EHF 540 all ...~ r~ d by the ~;~ cll; Rayon
Co~l)olaliol..
In FY~mrle 6, a version of the &~paraluD illuDll~tGd in Figure 4 was
motlifie~l to hang vertically down a 2 inch pipe and remove the kerosene from a
kerosGl.c/water ~-iAlUlC.
CA 02248280 1998-07-08
EXAMP~ 1
~GULAR MODUI~ F~UX '1~-1 - KE~ROOE~
% Open Fl~ers - 67.09%
3 0.431 1227 1.423 0.83
11 1.S8 2.454 0.776 VISC
21 3.017 3.681 0.61 l.g7
34 4.885 4.gO8 0.502 t~l ' '
Ihcte~t ~ conductcd-t30- CI ' ~ ,~ pr~ condition~t~bulated. Iheunit
~XAMPIE~ 2
REGULAR MODUI~ FIllX T3XT - DIE~EL
% Open Fl~ers - 67.09%
s~ ~sc.~.s~c.~.
;- S ~ cc~ccc3~3c~3~ ~cCc~ 3~... 3~ ~3~ C.~ .. ~C3~;
'~CS ~ ~ "C''? ~3~ i .3 ~............................................... ~ ; C. 0,~-3~
3;. ~ .. i~ C~- ~ ' ~,, ,~,, ,.~ . p ~ r ; ~07 ~C~3b '3
.3 ~ .'C .;-S ~ -.C~ ?~ -~ ~ 6
~ ; ~ . .. :i ::::: i ~. :~:: ~ ~ ' I ~ ~j3i k c ' ~ ~3'~ji ?~ ~, p~ :Sc '
CA 02248280 1998-07-08
~XAMPLE 3
WATE~ PRl~iUR~ DROP
14~
V~dq - 1.1709 ceatipobe (cP)
ri~
.... ~ ~ ~ t !~ ' '' h '' i: ::: :~:S ~, ~i: r, :.:;::.~:.S.i
~AMPLE 4
LlX-84
~ ~ q '~ rss~rsr
,j 5~ s- S",si~ .. 'i~.~.~ Y' ~ ~ Y~
,,,,,, ,~: ,,'P,',~ s .. s~ S s~ Ss
sssr~
CA 02248280 1998-07-08
~XAMPLE S
TREATM~NT OF ~ ~G CRUDE OIL
.................. ......... ....... ......................................
.s .~.~ s.~.. s,~
, ,~ ~ :1 ' '~ ' P ., Sl
~S 5~ ~ ,~ .!. ~.i, SS, ~ ~ i; S.r~.y.. :s::::.:.:.:.::~
. , ,,, ~"",~, ~:. P~ ~SS~ 'S ~ pj~ ;p~
i ; .P~ $.s;
ss ~ s;- ~ s ~
~ ss, i~ SSS-~ s ~; ~ . ~ ~; ,' ';:
,FS S .. ~ ~ S s . ~ ~ r .
::S'. i,"~ s~ ~ ~ ;SS s ~ s
S ~. S F ~ S3::, ~ f 3 ' .. S ~ ;., ~ S SS, . ' ~ ~J~ S
,,.~,~ ". .~: f S 'S ~ ', ,.. ; S S' '~'' f; :' :''S '3
3 ~ 's's'~ SSY~s'~ f,~f~ 'SS
.. c:., :;~ s:~ X~ s j ~ ;si :j' S 3 S ~ ,i
'SjSss ..;.si~~ S~ ,Y,;Sj~ 'SSC s~s~s~?~ s~g~
,S,j'j;~3'~ i3~'~ f~ sSiS3
~ompb S dbta u~ illwdnted t~buht4 dbp#d time, ~ tbe unwnt of oll
~oe~ved Jt the outlet of the modulc. In Jll ~utJoce~, the oil ~oelved Jt the outlet did not
h~ve u~ ~ee pba e ~ater ther~L
CA 02248280 1998-07-08
24
EXA~IE 6
....... ,............. , , ................. j . . ~.. ,,, , ........ ~... , .. ; .
5S:~S'.~i~' 5. ?'ij~ .~t ~; 5~,5~?~ 5~
.*:.?.~.:i ~i*?si ~ . ? ~ ' ~?;
,~ 5,S, i.s ' ~ t.,~ ";, 5, ,~ ~, S~ ' ' ; S~
Vbco.iq - 4.S cr
ID ~ample 6, ~ mi~ture of thc ~ P" J: n, ' rc-uiteJ in org~mic roc~ay
with no f~e pha e ~ter obu lved the~
EXAMP~ 7
METAL E~RACF~ONJSI~RlPPING
1. ~RACllON - A mi~ture ccoldin~ to the foUowin~ f ~ ~ t~tet 900 mm of met~i di~c t~te
iD 150 m of }e~eDe with SO ml ol LI~ CW~Dt. ~ ~ ~uit of the a~naioD, ~ d~ J o~
~u t~t.
A. n~; ~;!~;,~
5~ *s~r*i~* -s ~ S: ~.. : 5s.*. ~ s's'.~55.?s?.5.s. ~ ';s~; .. 5:.
.?i
D~ ~nrChd~nt
CA 02248280 1998-07-08
S~Urr~G-~mL~ d dkbnt~ ~ ~ H~04.A~tabuatoi~ ~ olt~oqpnk~ ~NoX~
S ~ ~ ~ ~
D~ ~ ~ -I~Ch ~t
Othx ~m~ we~ p~fonu~ f~m w~u a ~kq of ~ ~' of LoU~m, LUo~*~ ~-
D~HPA chel nt diuolvod in ~eno to V ~ nrieq d md~ f~m ~quo~ product ~dutbn~,
both gntbetic and Seld c~mpk~ Met l ' ~ ran~e f~m 40% to 100% per d l e; me~
ev lu ted includoi iron, ~ oDpper, nk~el nd zinc Orpnic V ' ~olution cont in no vi ible
~st~
I~LAMPIB 8
(~ANOIA OIL AND WAT~ MDCrUR~
In thi~ c~mple, S00 mL per minute of a 10 volume % clmola oil in water wa~ foi to tbe mK~duk ~t tbe ~bdl dde
inlet 128 The pre~ ure in the ~bdl wu ad~wltoi to p~dti~e S pd Tho fo~d I , wu 2S- C ~ a reullt
of tbe te t, tbe canola oil ro~ed containod no vidble water The ~nola oil wu ~lloctai from the fiber
lumen at p~int~ 126 and 124 u in Fgure 13A.
EXAMPIE~ 9
In thie e~ample, 426 mL min l of water at 2S- C wu foi to th~e mlodule et forth in E~mple 8 ~t 126, i~ the
feed wa~ - I down bore The re~ult of thie ~u tbat . . ~ 30 m~ m in~l of wator entered tbe ~hcll
through tbe Gb~x wall~ e~ting at the inlet and outlet 128 and 130 . '~ as indicated in Figure 13
~~ ' ~ there wa~ water ' ' ~' in the unit
CA 02248280 1998-07-08
;',.,~ S~,$$~ $~
s~S~ . .l;s~ s ,l~ $~i"S~
~ ~ ~s ~ ~' '' ' .~.l.~. , ~.
m
~,,ff ~}f~
3 ~ ~ ~ ~,,$'~,:o,' '~
~X:.$~ $.$
O ~ f ~u~f '~f ~
~; g ~ $ ~ $ $ ~ ; ~ - - - - - ~ ~ j3 ~
k$~ Y ~ $, $,ij.,.,.,.~ c:~; ~ %g,~$.$;~3 ~~
r$~.%~ :g~ ~ k $~:~3 k~ ;$ ~ ,3i,C; 3i~g~:%~$~ $:~
3~t$ l ~ Y ~ ~
::t.3$$.3$~%'.,$:3.3%""% j ' ~ :; ;%, f, ~ S%~#
g i' i~A~A''ii~'l' 'ilAiiiii~l~ i'i' ,~ t~ 3C. ~.~ C;~ /t~
" jj j ; t~ i' :i % ~ %, j~3 ~$,$,%,t j,$ :,,3 ' 'j;
'$?~ ~ ~, ~ ~,,,,5$, i.~ 't; ~ ' '; ' '%3~~
... t. ~ ~ ......
c.~ 'tt :.%:::~i3~i ' '' '"' '"'~i ~
'' "~ y,t3i~ :CC~y,$"3,,,~ ,f ~ ' ' '%; ~~$' ~'ft ~ g ~ i~,
ti t~, '~$% ... '~, '3~ "cs~c.3j$~ t::t::~tcc ~ "
~ %: . ?:~ : %s,: .~.:: :~., t, ,% : % ~ , ,:~
k,t kC ~ ~ ~---Y C$$~t# ~ 3"
CA 02248280 1998-07-08
These ~ les clearly illu~llale the .,l~e~ti.~..ess of the pr~sont
invention. In FY~mpl~ 8, the water flow rate of 450 ml per minute did not resultin any water brea~lhrou~ while, in col.lr~l, the flow rate of 426 ml min~1 down
bore caused water brea!~ll.lou~h in F~ 'e 9. Clearly, by pro.idin~E; a shell side
feed in accordAI~ce with the plesenl meth~3olr~cy~ water brea~lLrou~ll is not a
CQI~ . as in down bore feeding.
As tabulated in Table 1, s~ A"t Cl~A~g,f,S were noted in very
desirable physical and rh~ Al ~io~,lies of crude oil feeds d~...r l.-l~atGd for on-
site pilot tests at a variety of sites. By ~ g the crude oil feed to the hollow
fiber all~ and by ol~sel~i..~ a methodnlocy of the ~.eseilt In~e,nliOn,
some or all of ~h~sicocl-~--;rAl ~A~g~S in the plO ~llies of crude oils subsequent
to he~ . nt were obs~ ,d:
1. the oil was ~ *I~l;Ally anl.~drous;
2. decrease in oil density was obsel.ed;
3. a lower distillation t~ alule range was ol)sel~ed,
4. at least a re~ I ;on in the wax-out or tar d~,~osiliol~ in the ~,o.lu-;l;
5. a reJ-,~;t;~ n in liquid viscosity in substantially all of the examples;
6. a change in p~ li~,le size (for some oils, the change a~pe&~,d to be
a reduction in size);
7. an increase in API;
8. a decrease in some pour point te~l~llules and S~
ch~nges in the coll~ L.Iion erl;r;ef~ of the ploducl was ~.~ctel
and other chP ~;rAl ~ro~llies of the liquids are also ~,~cted
(these vary with p~ licle size); and
9. eMl~Pnt water from crude oil pilot runs were s~lit~le for relnjc-,lion
back into the wells.
CA 02248280 1998-07-08
28
As known in the art, enh~l.r:~g or reJ~c:~e suita~'e ~ro~lies of
a crude oil bGCO~l~f-S more v~llJ~lF and it is pos~ib'e to e~lu~ the ~oducl in abroader scope of a~ not known in the pAor art.
r~ plps 1, 2 and 4, show flux data for dirr.,ient organic liquids.
r~ c 3 shows m~ P, p~Gssur~ dropsholume H20 feed rate data fu~
~emn~ alil~g a zero break~ùu~ of water to the Ol~;~liC coll~,cti~n side of the
d~Jp~lU~. ~ample S shows lal~ldl~r data on a crude oil site del~r~dtion run.
FY~mp'- 6 ~e~..n.. l~dles that dry 01g ~ C pr~du.,l can be leco._led from a
vertically h~n~ing a~ g~ ..F~-t of less than about 2 inches about fli~mPter tubing;
this is useful for down hole or in-situ oil rec(,.e.~. FY~ ,IF 7 shows utility in
separation of metal rhplsntlor~ claqueous ~ lules; this is useful to the end of
achieving solvent extraction.
Table 1 tabulates the data from ~l,les 10 tl~rou~h 14 with
re..~c~t to v~i~us ~ ll,tel~ as ,..~9~ ued prior to h~,~t~n~ .~ (inlet data) andsubse.luent to lle~ lt (outlet data) for ~r~l~P of water in the ssmrle,
density, API grav-ity, pour point, flj~ tion and l~;.~.. ~t;c viscosil,~.
Generally, the ~,lotocol obsel~_d involved feP.~l;ne the sample at
desired rates and ~l~l;l;fu~c to the Q1lPll~ e of the fibers. In the table, the
t~,l...;l~nlcley ~inlet~ refers to the ~rcellLgP of water in the feed or the ~ ope.ties
of deh~dl~ted oil. ~Outlet~ refers to ~,e., ..lP~tecl oil.
In all i.~ n~f,s, the elllu~,nl aqueow phase was substantially oil free
and was sllit~hle for rçinjecti~n back into the rollllaliol. from which it came.
~ ;w.,s 13 tlllou~h 26 ~ hi~Ally illus~atP~ data from Table 1, and
in particular ~licle counts for an oil sample prior to lle~l...P.-t and subsequent
to tlG~ P~ .co,il~ le~l~lule charts in~lic~tin~ P...~tir viscosity as a
fimction of te~ tul~ for ~l~e~ l and post-lre~,..P- -I of the sample and
ASTM tli~ ti-~n data in~ Alil~e telll~cf~tw~ as a ~ln~tion of the fraction
CA 02248280 1998-07-08
~ -lle-l for v~,io-~s fractions in the oil prior to lleS~ t and ~l~.ent to
~e~ t accol~.ing to the ~--e~1-odolo~y of the prescnl i~ ,nlio,~.
Figure 13 illu~ les l &llicle dioll~ liO.~ for a crude oil sample
co~ g oil and water prior to lle~ with the hollow fiber methr)dolo~y as
set forth herein. It is clear that the l,~liclc size di~ ulio,l varies from
ap~ tP.ly 1 micron (~m) to ap~r~ t~ly 9 m..;,o~ m).
Figure 14 illu. ll~tcs the particle size d~ ulion after the sample
has been lreated with the fibers. It is clear that a ~ ,~licle size
distribution shift oc;ulled subsequent to the lre~ P~.t with the particle size
generally l~l een .01 lllic,l-ans (~um) to .1 ll.icrons (~m). This phr.u ... .~n has
been ~çm~ ..c~-~ted in the pastwhen oils have been subjected to a strong maerP,tie
field. This ~ e resulted in pcl...~..Pl.l particle disl.l~ulion shift.
The value of crude oil may be det~ .hled by an industry
equAl;~ti~. scale, the value being a f.~ t;--~- of the API. The scale ~l~r~;f;PS oil
in ~ nr~t API ranges. D~-~A;~g on the le.luhe...P~ c for the oil, the ranges in
API ~P~ A1in~n differ. Having regard to this dirrele.~ce, even a small increase in
API may be sllffir;~nt to çnhAnr,e the value of an oil to a higher c~e~
rigules 15 ~r~,u~l- 17 show a viscosity tem~latul~c chart in~ l;ug the
f ~-~Atir ~cosil~ of a crude oil sample as a r ~-ct;~ " of te~ lure~ an ASTMtmAtif)n ~.. ~.~ illui l~a~ g telu~ldlure data as a f l~-c~ of the rl.. clion
~lictille~l from the sample and a p~licle size and .]isllil)utioll graph for F~r~mr~-
10 and ~ir;rAlly at the ~et~ of a m~vle~ Similar Elflpl~ l repreS~.ntAti~nC
are set forth in r;it."es 21, ~ and 23 iilu llat~ng the same i.-fir..~..At;~
les~cctively but for the ~oull.,l~ i,.r~"..,At;..,. In the case of the ~r~ ge ofwater plcsellt in the sample subsequent to lle~ .1, the same went from 20.8%
to less than 0.01%, a ~;L;..;r;~ declezse in the density was Also -3. There was
an API gravity change of 0.3 as .--P~ u~d at 15.6- C and the pour point
subsequent to lle~ l increased 3- C Of rulll~. ~ A~ce, iS the distillation
CA 02248280 1998-07-08
and hr.P...-~;r viscosity data, where the boiling point in E~ample 10 d~opped 9-C subsequent to lre"l~..P -t with the ".~ ~ololD of the present in.~,nlion. A
c j~.,;r;,~ t dccr~ase in the l~;.. ..~t;r. viscosity was also noted, the inlet having an
~nsco:~ilr of 6.113 mm2s~ .. pS~red to the outlet value of 5.907 mm2s~l.
