CA2248280A1 - Organic recovery system and method - Google Patents

Abstract

There is disclosed a system for separating oil and other immiscible contaminants from a liquid body containing the contaminants such as a water body. The system includes the use of a plurality of microporous hollow fibers which may be arranged in any number of arrangements such as bundles, intersecting arrangements, divergent patterns or in a mat-like arrangement or a combination of the foregoing. The hollow fibers are in communications with a source of pressure in order to force the contaminant via the pores into the fibers for subsequent storage in a suitable container. By incorporating acceptable means of density control a substantial amount of the hollow fiber surface area may be exposed to the contaminant thus increasing the extraction efficiency of the contaminant from the water body. The unit optionally may be self-contained. Thissystem provides a substantial advantage over existing arrangements in that extraction efficiency is greatly enhanced in any number of environments. The system and methods are also useful in recovering crude oils, metals or other dissolved components, etc., from the aqueous phase.

Description

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 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.

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 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, 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

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.

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;

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 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 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~, 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~, 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., 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.

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, 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 .

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 ~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 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 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.

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.

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 ' ~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~

~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

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 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 ;',.,~ S~,$$~ $~

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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.

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 ~ -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 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.

Claims (25)

WE CLAIM:

1. A method of separating an immiscible organic compound from an aqueous mixture containing said compound and aqueous phase characterized in that said method comprises the steps of:
providing a plurality of hollow hydrophobic fibers having micropores therein and opposed ends inaccessible to said mixture, said micropores extending from the outside of each fiber to the hollow interior thereof;
pressurably forcing said mixture into contact with said micropores under sufficient pressure to only permit passage of said immiscible organic compound through said micropores and into said hollow interior, but insufficient for collapse of said fibers and passage of said aqueous phase;
collecting said immiscible organic compound; and discharging said aqueous phase substantially devoid of said immiscible organic compound.

2. The method as set forth in claim 1, characterized in that said fibers are isotropic fibers.

3. The method as set forth in claim 1, characterized in that said fibers are anisotropic fibers.

4. The method as set forth in claim 1, characterized in that said method further includes the step of recirculating said aqueous phase in the system.

5. The method as set forth in claim 1, characterized in that said method further includes the step of pretreating, in a pretreating step, said mixture prior to contact with said fibers.

6. The method as set forth in claim 5, characterized in that said pretreating step includes at least one of heating, filtration, centrifuging, cooling, freezing, dilution, precipitation or addition of chemical reagents and/or solvents or any combination of these for pretreatment of said mixture.

7. The method as set forth in claim 1, characterized in that said aqueous phase contains soil or sediment.

8. The method as set forth in claim 7, characterized in that said method further includes the step of percolating a solvent through said soil or sediment to dilute said organic compound and entrain said organic compound in said solvent.

9. The method as set forth in claim 5, characterized in that said method further includes the step of forcibly injecting into said soil or sediment, a solvent to entrain organic material in said solvent.

10. The method as set forth in claim 1, characterized in that said immiscible organic compound comprises an edible oil or an essential oil.

11. The method has set forth in claim 1, characterized in that said method is conducted in pressurized container or pressurizing said mixture.

12. The method as separating an immiscible organic compound from an aqueous mixture containing said compound and an aqueous phase, characterized in that said method comprises the steps of:
providing a plurality of hollow hydrophobic fibers having micropores therein and said fiber ends inaccessible to said mixture, said micropores extending from the outside of each fiber to the hollow interior thereof;
creating a pressure differential between said mixture and said hollow fibres such that said mixture is under higher pressure relative to said fibers, said pressure being sufficient to permit passage of said organic compound but insufficient to allow said aqueous phase passage into said micropores and for said hollow fibers to collapse;

contacting said micropores of said fibers with said mixtures;
collecting said immiscible organic compound; and discharging said aqueous phase substantially devoid of said immiscible \
organic compound.

13. The method as set forth in claim 12, characterized in that said organic compound comprises crude oil.

14. The method as set forth in claim 12, characterized in that said organic compound comprises oil and organometallic complex(es) to be recovered.

15. The method as set forth in claim 12, characterized in that said organic compound comprises edible oil or fixed oil.

16. The method as set forth in claim 12, characterized in that said hollow fibers comprise anisotropic fibers or isotropic fibers.

17. a method of altering the physicochemical properties of crude oil, said properties including at least one of liquid viscosity, density, particle size, API
rating, pour point, distillation characteristic and combustion efficiency characteristic, characterized in that said method comprises the step of:
providing a feed containing crude oil;
providing a polymeric matrix having pores therethrough for passing said crude oil;
forming a pressure differential across said matrix such that said pressure is sufficient to permit passage of said oil through said micropores, but insufficient for collapse of said matrix;
collecting said oil, said oil having at least one altered physicochemical property.

18. The method as set forth in claim 17, characterized in that said matrix comprises a matrix with a high oil flux.

15.

19. The method as set forth in claim 17, characterized in that said method further includes the step of removing any free water phase present in said crude oil prior to passage through said matrix.

20. The method as set forth in claim 17, characterized in that said matrix includes micropores having a diameter from about 0.03 microns (µm) to about 5 microns (µm).

21. The method as set forth in claim 20, characterized in that said matrix comprises isotropic hollow fibers or anisotropic hollow fibers.

22. The method as set forth in claim 17, characterized in that said matrix comprises a hydrophobic matrix or a hydrophilic matrix.

23. The method as set forth in claim 22, characterized in that passage of said crude oil through say hydrophobic matrix produces an organic mixture having altered physicochemical properties and a separate and discrete aqueous phase substantially devoid of said crude oil.

24. The method as set forth in claim 17, characterized in that said polymeric matrix comprises an oleophilic polymer.

25. The method as set forth in claim 17, characterized in that said matrix having pores therethrough for selectively passing said crude oil.